WO2012141783A1 - Oléfines et procédés de fabrication desdites oléfines - Google Patents

Oléfines et procédés de fabrication desdites oléfines Download PDF

Info

Publication number
WO2012141783A1
WO2012141783A1 PCT/US2012/024922 US2012024922W WO2012141783A1 WO 2012141783 A1 WO2012141783 A1 WO 2012141783A1 US 2012024922 W US2012024922 W US 2012024922W WO 2012141783 A1 WO2012141783 A1 WO 2012141783A1
Authority
WO
WIPO (PCT)
Prior art keywords
olefin
mono
less
feedstock
olefinic
Prior art date
Application number
PCT/US2012/024922
Other languages
English (en)
Other versions
WO2012141783A4 (fr
Inventor
Nicholas Ohler
Karl Fisher
Jin Ki Hong
Original Assignee
Amyris, Inc.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Amyris, Inc. filed Critical Amyris, Inc.
Priority to BR112013026417-9A priority Critical patent/BR112013026417B1/pt
Priority to US14/112,235 priority patent/US10294439B2/en
Priority to EP12708189.1A priority patent/EP2697187B1/fr
Publication of WO2012141783A1 publication Critical patent/WO2012141783A1/fr
Publication of WO2012141783A4 publication Critical patent/WO2012141783A4/fr
Priority to US16/389,690 priority patent/US11193078B2/en
Priority to US17/518,540 priority patent/US11802100B2/en
Priority to US18/371,412 priority patent/US20240043356A1/en

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
    • C07C5/02—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation
    • C07C5/03—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of non-aromatic carbon-to-carbon double bonds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
    • C07C5/02—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation
    • C07C5/03—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of non-aromatic carbon-to-carbon double bonds
    • C07C5/05—Partial hydrogenation
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/04—Liquid carbonaceous fuels essentially based on blends of hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M105/00—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound
    • C10M105/02—Well-defined hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M105/00—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound
    • C10M105/02—Well-defined hydrocarbons
    • C10M105/04—Well-defined hydrocarbons aliphatic
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M107/00—Lubricating compositions characterised by the base-material being a macromolecular compound
    • C10M107/02—Hydrocarbon polymers; Hydrocarbon polymers modified by oxidation
    • C10M107/14—Hydrocarbon polymers; Hydrocarbon polymers modified by oxidation containing conjugated diens
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2521/00—Catalysts comprising the elements, oxides or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium or hafnium
    • C07C2521/02—Boron or aluminium; Oxides or hydroxides thereof
    • C07C2521/04—Alumina
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals
    • C07C2523/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals of the platinum group metals
    • C07C2523/44—Palladium
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
    • C07C2523/74—Iron group metals
    • C07C2523/75—Cobalt
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
    • C10M2203/003—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions used as base material
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
    • C10M2203/02—Well-defined aliphatic compounds
    • C10M2203/0206—Well-defined aliphatic compounds used as base material
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
    • C10M2203/02—Well-defined aliphatic compounds
    • C10M2203/022—Well-defined aliphatic compounds saturated
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
    • C10M2203/02—Well-defined aliphatic compounds
    • C10M2203/024—Well-defined aliphatic compounds unsaturated
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
    • C10M2205/08—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing non-conjugated dienes
    • C10M2205/083—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing non-conjugated dienes used as base material
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/582—Recycling of unreacted starting or intermediate materials

Definitions

  • feedstocks derived from an alkene comprising a conjugated diene moiety and one or more additional olefinic bonds methods of making the feedstocks and methods of their use.
  • the feedstocks described herein may be used to replace or to supplement olefinic feedstocks derived from fossil fuels.
  • the alkene used to make the feedstocks is derived from a renewable carbon source.
  • Olefins can be used as raw materials or feedstocks in a variety of industrial processes, such as in the production of plastics, fatty acids, detergents, oils, and the like.
  • Conventional olefinic feedstocks are often derived from petroleum or petroleum products.
  • olefins are derived from cracking of petroleum as hydrocarbon streams that are mixtures of olefins, saturated hydrocarbons, and oxygenates.
  • mixtures of alpha olefins and internal olefins having a broad range of carbon numbers are produced by catalytic oligomerization of ethylene or propylene (either of which is typically derived from petroleum).
  • substantial downstream processing can be required to isolate a desired product from a mixture, e.g.
  • olefins derived by cracking or through oligomerization of ethylene or propylene is highly catalyst dependent and can vary from batch to batch in some cases.
  • Olefins produced from petroleum can contain sulfur and aromatic compounds, which are environmentally undesirably impurities.
  • olefinic feedstocks e.g. olefinic feedstocks that include no detectable amounts of sulfur or aromatic compounds.
  • methylated olefinic feedstocks e.g. methylated olefinic feedstocks in which the methylation position is controlled.
  • olefinic feedstocks comprising partially hydrogenated conjugated alkenes, methods for making the same, methods of using the olefinic feedstocks described herein in manufacture, and products produced by the methods of use.
  • certain methods provided herein are capable of selectively hydrogenating particular olefinic bond(s) of a conjugated alkene to yield mono-olefinic feedstocks.
  • the olefinic (e.g., mono- olefinic) feedstocks comprise little or no contaminants.
  • the olefinic feedstocks are made from a conjugated alkene comprising at least one conjugated diene and at least one additional olefinic bond.
  • the conjugated alkene in a first stage, is reacted with hydrogen in the presence of a first catalyst under conditions suitable to preferentially hydrogenate at least one of the olefinic bonds in the conjugated diene to produce a partially hydrogenated olefinic intermediate in a first stage.
  • catalysts and conditions such as catalyst loading, catalysis temperatures and catalysis presssure, are described in detail herein.
  • a partially hydrogenated intermediate is reacted with hydrogen in the presence of a second catalyst under conditions suitable for making the desired olefinic feedstock.
  • catalysts and conditions such as catalyst loading, catalysis temperatures and catalysis presssure, and resulting olefinic feedstocks are described herein.
  • the first catalyst and the second catalyst are the same. In other embodiments, the first catalyst and the second catalyst are different.
  • the conjugated alkene can be any conjugated alkene apparent to one of skill in the art.
  • the conjugated alkene comprises the conjugated diene and at least one additional olefinic bond.
  • the conjugated alkene comprises the conjugated diene and at least two additional olefinic bonds.
  • the conjugated alkene comprises the conjugated diene and at least three additional olefinic bonds.
  • the conjugated alkene comprises an alpha-olefinic bond.
  • the conjugated diene comprises an alpha- olefinic bond.
  • the conjugated alkene is a Cio-C 30 alkene.
  • the conjugated alkene is a terpene.
  • exemplary terpenes include myrcene, ocimene and farnesene.
  • the conjugated terpene is ⁇ -farnesene and/or a-farnesene.
  • methods described herein comprise selectively hydrogenating a conjugated terpene comprising at least three olefinic bonds wherein two of the at least three olefinic bonds form a conjugated diene, to make a composition comprising at least about 65% mono-olefinic species (e.g., at least about 65%, at least about 70%, at least about 75%, or at least about 80%).
  • a conjugated terpene comprising at least three olefinic bonds wherein two of the at least three olefinic bonds form a conjugated diene
  • methods described herein comprise selectively hydrogenating a conjugated terpene comprising at least three olefinic bonds wherein two of the at least three olefinic bonds form a conjugated diene, to make a composition comprising at least about 50% mono-olefinic species and at most about 10% di-olefinic species.
  • the methods are capable of producing a composition comprising at least about 50%, at least about 60%, at least about 70%, or at least about 80% mono-olefin and at most about 5% di- olefin.
  • the methods are capable of producting a composition comprising at least about 50%, at least about 60%, at least about 70%, or at least about 80% mono-olefin and at most about 3%, at most about 2%, at most about 1%, or at most about 0.5% di-olefin.
  • the compositions produced by selective hydrogenation of conjugated terpenes comprise about 1% or less, about 0.5% or less, or about 0.1% or less conjugated diene.
  • the conjugated alkene (e.g., terpene) is produced by one or more microorganisms.
  • the conjugated alkane can be produced by a bioengineered microorganism, i.e. a microorgamism engineered to produce the conjugated alkane starting material, or a precursor thereof.
  • the microorganism produces the conjugated alkane, or a precursor thereof, from a renewable carbon source.
  • the present methods provide renewable sources for the resulting olefinic feedstocks.
  • the resulting olefinic feedstocks comprise a substantial amount of a mono-olefinic partially hydrogenated conjugated alkene.
  • the feedstocks comprise a limited amount of the corresponding alkane.
  • the feedstocks comprise a limited amount of corresponding species having two or more double bonds.
  • the feedstocks comprise a limited amount of the corresponding conjugated alkene.
  • the resulting olefinic feedstocks are rich in mono-olefinic species.
  • the resulting olefinic feedstocks are rich in mono-olefinic species and contain limited amounts of corresponding di- olefinic species.
  • the olefinic feedstocks comprise at least about 60% mono-olefin, at least about 65% mono-olefin, at least about 70% mono-olefin, at least about 75% mono-olefin, at least about 80% mono-olefin or at least about 85% mono-olefin. In certain embodiments, the olefinic feedstocks comprise less than about 25% alkane, less than about 20% alkane, less than about 15% alkane or less than about 10% alkane.
  • the olefinic feedstocks comprise about 15% or less di-olefinic species, e.g., about 10% or less, about 9% or less, about 8% or less, about 7% or less, about 6% or less, about 5% or less, about 4% or less, about 3% or less, about 2% or less, or about 1% or less di- olefins.
  • di-olefins that are present are predominantly unconjugated dienes.
  • the olefinic feedstocks comprise less than about 25% conjugated alkene, less than about 20% conjugated alkene, less than about 15% conjugated alkene, less than about 10% conjugated alkene, less than about 5% conjugated alkene, or less than about 2% conjugated alkene.
  • the olefinic feedstocks have little or no sulfur or aromatic content. In certain embodiments, the olefinic feedstocks have little or no sulfur content. In certain embodiments, the olefinic feedstocks have little or no aromatic content. In certain embodiments, the olefinic feedstocks have little or no sulfur content and little or no aromatic content. Exemplary amounts of sulfur and/or aromatic content are provided herein.
  • partially hydrogenated olefmic feedstocks comprising a substantial amount of a partially hydrogenated conjugated alkene and a limited amount of the
  • the partially hydrogenated olefmic feedstocks comprise a limited amount of the conjugated alkene starting material.
  • partially hydrogenated olefmic feedstocks comprising a substantial amount of mono-olefinic species and a limited amount of di-olefinic species.
  • partially hydrogenated olefmic feedstocks comprising a substantial amount of mono-olefinic species, a limited amount of corresponding alkane and little or or sulfur or aromatic content.
  • feedstocks comprising a substantial amount of mono-olefinic species, a limited amount of corresponding di-olefinic species and little or no sulfur or aromatic content.
  • the feedstocks are prepared according to the methods described herein.
  • the olefmic feedstocks described herein may comprise one or more methylated alkenes (e.g. one or more of methylated mono-alkenes, methylated di-alkenes, methylated tri-alkenes, and methylated tetra-alkenes, where the number of carbon atoms in the base alkene for any of the above corresponds to the number of carbon atoms in the main chain of the hydrocarbon terpene used to make the feedstock).
  • methylated alkenes e.g. one or more of methylated mono-alkenes, methylated di-alkenes, methylated tri-alkenes, and methylated tetra-alkenes, where the number of carbon atoms in the base alkene for any of the above corresponds to the number of carbon atoms in the main chain of the hydrocarbon terpene used to make the feedstock.
  • An olefmic feedstock described herein that comprises partially hydrogenated conjugated alkene can exhibit a narrow molecular weight distribution as produced (e.g. a distribution spanning over about 2- 10 amu), without requiring a separation process such as distillation.
  • An olefmic feedstock described herein that is derived from more than one conjugated alkene can exhibit a broader but predicted molecular weight distribution as produced, again without the need for a separation process.
  • the olefmic feedstocks provided herein are mixed olefmic feedstocks.
  • the olefmic feedstocks provided herein can further comprise, for example, a second partially hydrogenated conjugated alkene.
  • the olefmic feedstocks provided herein may further comprise a linear alpha olefin, a branched alpha olefin, a linear internal olefin or a branched internal olefin.
  • compositions prepared according to any of the methods described herein are provided.
  • the olefmic feedstocks can be used for any purpose apparent to one of skill in the art.
  • the olefmic feedstocks can be used for the preparation of a plastic, a detergent, a lubricant, an oil, or another product desired by one of skill in the art.
  • an olefmic feedstock provided herein can supplement a conventional olefmic feedstock derived from fossil fuel in any process deemed suitable by one of skill in the art.
  • the olefmic feedstock can replace a conventional olefmic feedstock derived from fossil fuel deemed suitable by one of skill in the art.
  • the olefmic feedstocks described herein can be polymerized, oligomerized, copolymerized, or co-oligomerized to make, for example, an oil or lubricant.
  • products e.g. plastics, oils, or alcohols
  • an industrial process e.g. , oligomerization, polymerization, hydroformylation, carbonylation, and the like
  • methods that comprise using an olefinic feedstock comprising a partially hydrogenated Cio-C 30 hydrocarbon terpene as a monomer or reactant in an industrial process
  • FIGURE 1 provides a GC-MS spectrum of ⁇ -farnesene that is 71% hydrogenated.
  • FIGURE 2 provides a GC-MS spectrum of ⁇ -farnesene that is 78% hydrogenated.
  • FIGURE 3 provides a l H NMR spectrum of ⁇ -farnesene that is 25% hydrogenated.
  • FIGURE 4A provides a reaction profile for Example 23.
  • FIGURE 4B provides a reaction profile for Example 25.
  • FIGURES 5 A-5F provide plots of experimental results for Examples 16-31.
  • FIGURE 5A shows % mono-olefin vs. % di-olefin.
  • FIGURE 5B shows % di-olefin vs. % farnesane.
  • FIGURE 5C shows % mono-olefm vs. % farnesane.
  • FIGURE 5D shows % mono-olefin vs. second stage hydrogenation temperature (°C).
  • FIGURE 5E shows % farnesane vs. second stage hydrogenation temperature (°C).
  • FIGURE 5F shows % di-olefin vs. second stage hydrogenation temperature (°C).
  • FIGURE 6 provides a diagram of a fixed bed reactor used in Example 32.
  • FIGURES 7A-7C provides graphs of populations of various species as hydrogenation proceeds in a second stage for Example 34.
  • Second stage hydrogenation conditions for the data shown in FIGURE 7A are 200°C, 2 bar hydrogen pressure;
  • second stage hydrogenation conditions for the data shown in FIGURE 7B are 200°C, 1 bar hydrogen pressure;
  • second stage hydrogenation conditions for the data shown in FIGURE 7C are 200°C, 0.5 bar hydrogen pressure.
  • "X" represents farnesene content, solid squares represent mono-olefin content, solid triangles represent di-olefin content, and solid diamonds represent farnesane content.
  • a conjugated alkene as used herein encompasses an alkene (which may by linear or branched, acyclic or cyclic) comprising at least one conjugated diene moiety. It should be noted that the conjugated diene may have any stereochemistry (e.g. , cis or trans) and the conjugated diene may be part of a longer conjugated segment of the alkene, e.g., the conjugated diene moiety may be part of a conjugated triene.
  • Terpene as used herein is a compound that is capable of being derived from isopentyl pyrophosphate (IPP) or dimethylallyl pyrophosphate (DMAPP), and the term terpene encompasses hemiterpenes, monoterpenes, sesquiterpenes, diterpenes, sesterterpenes, triterpenes, tetraterpenes and polyterpenes.
  • a hydrocarbon terpene contains only hydrogen and carbon atoms and no heteroatoms such as oxygen, and in some embodiments has the general formula (C 5 H 8 ) n , where n is 1 or greater.
  • conjugated terpene or “conjugated hydrocarbon terpene” as used herein refers to a terpene comprising at least one conjugated diene moiety. It should be noted that the conjugated diene moiety of a conjugated terpene may have any stereochemistry (e.g. , cis or trans) and may be part of a longer conjugated segment of a terpene, e.g. , the conjugated diene moiety may be part of a conjugated triene moiety.
  • hydrocarbon terpenes as used herein also encompasses monoterpenoids, sesquiterpenoids, diterpenoids, triterpenoids, tetraterpenoids and polyterpenoids that exhibit the same carbon skeleton as the corresponding terpene but have either fewer or additional hydrogen atoms than the corresponding terpene, e.g., terpenoids having 2 fewer, 4 fewer, or 6 fewer hydrogen atoms than the corresponding terpene, or terpenoids having 2 additional, 4 additional or 6 additional hydrogen atoms than the corresponding terpene.
  • conjugated hydrocarbon terpenes include isoprene, myrcene, a-ocimene, ⁇ -ocimene, a-farnesene, ⁇ -farnesene, ⁇ -springene, geranylfarnesene, neophytadiene, cw-phyta-l,3-diene, iraws-phyta- 1,3 -diene, isodehydrosqualene, isosqualane precursor I, and isosqualane precursor II.
  • terpene and isoprenoids are used interchangeably herein, and are a large and varied class of organic molecules that can be produced by a wide variety of plants and some insects.
  • Some terpenes or isoprenoid compounds can also be made from organic compounds such as sugars by microorganisms, including bioengineered microorganisms. Because terpenes or isoprenoid compounds can be obtained from various renewable sources, they are useful monomers for making eco-friendly and renewable base oils.
  • the conjugated hydrocarbon terpenes as described herein are derived from microorganisms using a renewable carbon source, such as a sugar.
  • Myrcene refers to a compound having the following structure:
  • Optimene refers to a-ocimene, ⁇ -ocimene or a mixture thereof.
  • a-ocimene refers to a compound having the following formula: or a stereoisomer thereof.
  • ⁇ -ocimene refers to a compound having the following formula:
  • Tarnesene refers to a-farnesene, ⁇ -farnesene or a mixture thereof.
  • a-Farnesene refers to a compound having the following structure: or a stereoisomer (e.g., s-cis isomer) thereof.
  • a-farnesene comprises a substantially pure stereoisomer of a-farnesene.
  • a-farnesene comprises a mixture of
  • stereoisomers such as s-cis and s-trans isomers.
  • the amount of each of the stereoisomers in an ⁇ -farnesene mixture is independently from about 0.1 wt. % to about 99.9 wt. %, from about 0.5 wt. % to about 99.5 wt. %, from about 1 wt. % to about 99 wt. %, from about 5 wt. % to about 95 wt. %, from about 10 wt. % to about 90 wt. % or from about 20 wt. % to about 80 wt. %, based on the total weight of the ⁇ -farnesene mixture of stereoisomers.
  • ⁇ -farnesene refers to a compound having the following structure: or a stereoisomer thereof.
  • ⁇ -farnesene comprises a substantially pure stereoisomer of ⁇ -farnesene.
  • substantially pure ⁇ -farnesene refers to compositions comprising at least 80%, at least 90%, at least 95%, at least 97%, at least 98% or at least 99% ⁇ -farnesene by weight, based on total weight of the farnesene.
  • ⁇ -farnesene comprises a mixture of stereoisomers, such as s-cis and s-trans isomers.
  • the amount of each of the stereoisomers in a ⁇ -farnesene mixture is independently from about 0.1 wt. % to about 99.9 wt. %, from about 0.5 wt. % to about 99.5 wt. %, from about 1 wt. % to about 99 wt. %, from about 5 wt. % to about 95 wt. %, from about 10 wt. % to about 90 wt. %, or from about 20 wt. % to about 80 wt. %, based on the total weight of the ⁇ -farnesene mixture of stereoisomers.
  • Frnesane refers to a compound having the following structure: or a stereoisomer thereof.
  • ⁇ -springene refers to a compound having the following structure:
  • Neophytadiene refers to a compound having the following structure:
  • rra «,y-phyta-l,3-diene refers to a compound having the following structure:
  • Czs-phyta- 1,3-diene refers to a compound having the following structure:
  • isodehydrosqualene refers to a compound having the following structure:
  • isosqualane precursor I or 2,6, 18,22-tetramethyl- 10-methylene- 14- vinyltricosa-2,6, 1 1, 17,21 -pentaene refers to a compound having the following structure:
  • isosqualane precursor ⁇ or 2,6, 14,18,22-pentamethyl- 10-vinyltricosa- 2,6, 10, 14, 17,21 -pentaene refers to a compound having the following structure:
  • Geranylfarnesene refers to a compound having the following structure:
  • Hydrogenated myrcene refers to a myrcene molecule in which at least one carbon-carbon double bond is hydrogenated. Hydrogenated myrcene encompasses myrcene in which one, two, or three double bonds are hydrogenated, and any mixtures thereof. Partially hydrogenated myrcene refers to a myrcene molecule in which only one or two double bonds have been hydrogenated, and also refers to a hydrogenated myrcene sample in which at least about 5% of the carbon-carbon double bonds remain unsaturated. A sample of partially hydrogenated myrcene may comprise dihydromyrcene,
  • hydrogenated myrcene sample comprises myrcene in addition to one or more of dihydromyrcene, tetrahydromyrcene, and hexahydromyrcene.
  • Hydrogenated ocimene refers to an ocimene molecule in which at least one carbon-carbon double bond is hydrogenated. Hydrogenated ocimene encompasses ocimene in which one, two, or three double bonds are hydrogenated, and any mixtures thereof. Partially hydrogenated ocimene refers to an ocimene molecule in which only one or two double bonds have been hydrogenated, and also refers to a hydrogenated ocimene sample in which at least about 5% of the carbon-carbon double bonds remain unsaturated. A sample of partially hydrogenated ocimene may comprise dihydroocimene,
  • hydrogenated ocimene sample comprises ocimene in addition to one or more of dihydroocimene, tetrahydroocimene, and hexahydroocimene.
  • Hydrogenated famesene refers to famesene (e.g. ⁇ -farnesene or a-famesene) wherein at least one carbon-carbon double bond is hydrogenated. Hydrogenated famesene encompasses ⁇ -farnesene or ⁇ -famesene in which one, two, three or four double bonds are hydrogenated, and any mixtures thereof. Hydrogenated famesene is obtained by complete or partial hydrogenation of famesene, and encompasses famesane. Partially hydrogenated famesene refers to famesene (e.g.
  • ⁇ -farnesene or ⁇ -famesene in which one, two, or three double bonds are hydrogenated, and any mixture thereof.
  • Partially hydrogenated famesene refers to a famesene molecule in which only one, two or three double bonds have been hydrogenated, and also refers to a hydrogenated famesene sample in which at least about 5% of the carbon-carbon double bonds remain unsaturated.
  • a sample of partially hydrogenated famesene may include famesene in addition to one or more of dihydrofamesene, tetrahydrofamesene,
  • R k R L +k*(R u -R L ), wherein k is a variable ranging from 1% to 100% with a 1% increment, i.e., k is 1 percent, 2 percent, 3 percent, 4 percent, 5 percent, ..., 50 percent, 51 percent, 52 percent, ..., 95 percent, 96 percent, 97 percent, 98 percent, 99 percent, or 100 percent.
  • any numerical range defined by any two numbers R k as defined above is also specifically disclosed herein.
  • a reaction that is “substantially complete” means that the reaction contains more than about 80% desired product by percent yield, more than about 90% desired product by percent yield, more than about 95% desired product by percent yield, or more than about 97% desired product by percent yield.
  • a reactant that is “substantially consumed” means that more than about 85%, more than about 90%, more than about 95%, more than about 97% of the reactant has been consumed, by weight%, or by mol%.
  • a composition that consists "predominantly" of a component refers to a composition comprising 60% or more of that component, unless indicated otherwise.
  • a composition that "consists essentially of a component refers to a composition comprising 80% or more of that component, unless indicated otherwise.
  • % refers to % measured as wt. % or as area % by GC-MS or GC-FID, unless specifically indicated otherwise.
  • partial hydrogenation of alkenes comprising multiple carbon-carbon double bonds results in a mixture of species, e.g., a mixture comprising a statistically determined distribution of partially hydrogenated and completely hydrogenated species.
  • a mixture of species e.g., a mixture comprising a statistically determined distribution of partially hydrogenated and completely hydrogenated species.
  • described herein are methods for partial hydrogenation of conjugated alkenes in which the distribution of species in the final partially hydrogenated product is other than expected by statistical considerations.
  • partial hydrogenation methods that produce i) essentially tri-olefinic species with limited amounts of alkane and conjugated diene (referred to herein as a tri-olefinic feedstock); ii) a mixture comprising predominantly a mixture of di-olefinic and mono-olefinic species with limited amounts of alkane, and little or no conjugated diene; iii) at least about 50% mono-olefinic species with limited amounts of alkane, limited amounts of di-olefinic species, limited amounts of tri-olefinic species, and little or no conjugated diene (referred to herein as a mono-olefinic feedstock); or iv) at least about 50% mono-olefinic species with limited amounts of di-olefinic species (e.g., unconjugated di-olefinic species) (also referred to herein as a mono-olefinic feedstock).
  • a tri-olefinic feedstock e.g., a mixture comprising
  • the olefmic feedstocks are derived from a conjugated alkene.
  • the conjugated alkene can be cyclic or acyclic, linear or branched.
  • the conjugated alkene generally comprises at least a conjugated diene.
  • the conjugated alkene can further comprise one or more additional olefmic bonds.
  • the conjugated alkene further comprises one, two, three, four or more than four additional olefmic bonds.
  • the conjugated alkene is a Cio-C 30 conjugated alkene. In certain embodiments, the conjugated alkene is a terpene. In certain embodiments, the terpene is a C 10 -C30 terpene. In certain embodiments, the terpene is selected from the group consisting of a monoterpene, a sesquiterpene, a diterpene, a triterpene and any combination thereof.
  • the olefmic feedstocks are derived from myrcene, ocimene, farnesene, springene, geranylfarnesene, isodehydrosqualene, isosqualane precursor I, or isosqualane precursor II.
  • an olefmic feedstock is derived from a single conjugated hydrocarbon terpene, e.g. a C 10 -C30 conjugated hydrocarbon terpene such as myrcene, ocimene, farnesene, springene, geranylfarnesene, isodehydrosqualene, isosqualane precursor I, or isosqualane precursor II.
  • a single conjugated hydrocarbon terpene e.g. a C 10 -C30 conjugated hydrocarbon terpene such as myrcene, ocimene, farnesene, springene, geranylfarnesene, isodehydrosqualene, isosqualane precursor I, or isosqualane precursor II.
  • an olefmic feedstock is derived from two or more conjugated hydrocarbon terpenes (e.g., an olefmic feedstock produced by partial hydrogenation of a mixture of two or more hydrocarbon terpenes, an olefmic feedstock comprising a mixture of two or more partially hydrogenated hydrocarbon terpenes, or an olefmic feedstock comprising two or more co-feeds, where one co-feed comprises a first partially hydrogenated terpene and another co-feed comprises a different partially hydrogenated terpene).
  • the olefmic feedstock is derived from farnesene, e.g. ⁇ -farnesene and/or a-farnesene.
  • the olefmic feedstock is derived from a mixture of farnesene (e.g., ⁇ -farnesene and/or a- farnesene) and myrcene.
  • the conjugated terpenes disclosed herein may be obtained from any suitable source.
  • the conjugated terpene is obtained from naturally occurring plants or marine species.
  • farnesene can be obtained or derived from naturally occurring terpenes that can be produced by a variety of plants, such as Copaifera langsdorfii, conifers, and spurges; or by insects, such as swallowtail butterflies, leaf beetles, termites, or pine sawflies; and marine organisms, such as algae, sponges, corals, mollusks, and fish.
  • Terpene oils can also be obtained from conifers and spurges.
  • Conifers belong to the plant division Pinophya or Coniferae and are generally cone-bearing seed plants with vascular tissue. Conifers may be trees or shrubs. Non-limiting examples of suitable conifers include cedar, cypress, douglas fir, fir, juniper, kauris, larch, pine, redwood, spruce and yew.
  • Spurges also known as Euphorbia, are a diverse worldwide genus of plants belonging to the spurge family (euphorbiaceae). Farnesene is a sesquiterpene, a member of the terpene family, and can be derived or isolated from terpene oils for use as described herein.
  • a conjugated terpene is derived from a fossil fuel (petroleum or coal), for example, by fractional distillation of petroleum or coal tar.
  • a conjugated terpene is made by chemical synthesis.
  • suitable chemical synthesis of farnesene includes dehydrating nerolidol with phosphoryl chloride in pyridine as described in the article by Anet E.F.L.J., "Synthesis of ( ⁇ , ⁇ )- ⁇ -, and (Z)-P-farnesene", Aust. J. Chem. 23(10), 2101- 2108, which is incorporated herein by reference in its entirety.
  • 4,546, 1 which is incorporated herein by reference in its entirety, describes synthesis of a mixture of (E)-P-farnesene and (Z)-P-farnesene from nerolidol.
  • Farnesol or nerolidol may be converted into a-farnesene or ⁇ -farnesene, or a combination thereof by dehydration with a dehydrating agent or an acid catalyst.
  • Any suitable dehydrating agent or acid catalyst that can convert an alcohol into an alkene may be used.
  • suitable dehydrating agents or acid catalysts include phosphoryl chloride, anhydrous zinc chloride, phosphoric acid, and sulfuric acid.
  • a conjugated terpene is obtained using genetically modified organisms that are grown using renewable carbon sources (e.g., sugar cane).
  • a conjugated terpene is prepared by contacting a cell capable of making a conjugated terpene with a suitable carbon source under conditions suitable for making a conjugated terpene.
  • suitable carbon source e.g., sugar cane.
  • any carbon source that can be converted into one or more isoprenoid compounds can be used herein.
  • the carbon source is a fermentable carbon source (e.g., sugars), a non- fermentable carbon source or a combination thereof.
  • a non- fermentable carbon source is a carbon source that cannot be converted by an organism into ethanol.
  • suitable non-fermentable carbon sources include acetate, glycerol, lactate and ethanol.
  • the sugar can be any sugar known to one of skill in the art.
  • the sugar is a monosaccharide, disaccharide, polysaccharide or a combination thereof.
  • the sugar is a simple sugar (a monosaccharide or a disaccharide).
  • suitable monosaccharides include glucose, galactose, mannose, fructose, ribose and combinations thereof.
  • suitable disaccharides include sucrose, lactose, maltose, trehalose, cellobiose, and combinations thereof.
  • the sugar is sucrose.
  • the carbon source is a polysaccharide.
  • suitable polysaccharides include starch, glycogen, cellulose, chitin, and combinations thereof.
  • the sugar suitable for making a conjugated terpene can be obtained from a variety of crops or sources.
  • suitable crops or sources include sugar cane, bagasse, miscanthus, sugar beet, sorghum, grain sorghum, switchgrass, barley, hemp, kenaf, potato, sweet potato, cassava, sunflower, fruit, molasses, whey, skim milk, corn, stover, grain, wheat, wood, paper, straw, cotton, cellulose waste, and other biomass.
  • suitable crops or sources include sugar cane, sugar beet and corn.
  • the sugar source is cane juice or molasses.
  • a conjugated terpene can be prepared in a facility capable of biological manufacture of isoprenoids.
  • the facility may comprise any structure useful for preparing Ci 5 isoprenoids (e.g., a-farnesene, ⁇ -farnesene, nerolidol or farnesol) using a microorganism capable of making the Ci 5 isoprenoids with a suitable carbon source under conditions suitable for making the Ci 5 isoprenoids.
  • the biological facility comprises a cell culture comprising a desired isoprenoid (e.g., a C 5 , Cio, a Ci 5 , a C20, or a C25 isoprenoid) in an amount of at least about 1 wt. %, at least about 5 wt. %, at least about 10 wt. %, at least about 20 wt. %, or at least about 30 wt. %, based on the total weight of the cell culture.
  • the biological facility comprises a fermentor comprising one or more cells capable of generating a desired isoprenoid. Any fermentor that can provide for cells or bacteria a stable and optimal environment in which they can grow or reproduce may be used herein.
  • the fermentor comprises a culture comprising one or more cells capable of generating a desired isoprenoid (e.g., a Cio, a C15, a C 20 , or a C25 isoprenoid).
  • a desired isoprenoid e.g., a Cio, a C15, a C 20 , or a C25 isoprenoid.
  • the fermentor comprises a cell culture capable of biologically manufacturing farnesyl pyrophosphate (FPP).
  • the fermentor comprises a cell culture capable of biologically manufacturing isopentenyl diphosphate (IPP).
  • the fermentor comprises a cell culture comprising a desired isoprenoid (e.g., a Cio, a C15, a C20, or a C25 isoprenoid) in an amount of at least about 1 wt. %, at least about 5 wt. %, at least about 10 wt. %, at least about 20 wt.
  • the facility may further comprise any structure capable of manufacturing a chemical derivative from the desired isoprenoid (e.g., a C 5 , Cio, a C15, a C20, or a C25 isoprenoid).
  • a facility comprises a reactor for dehydrating nerolidol or farnesol to a-farnesene or ⁇ - farnesene or a combination thereof.
  • a facility comprises a reactor for dehydrating linalool to myrcene or ocimene or a combination thereof. Any reactor that can be used to convert an alcohol into an alkene under conditions known to skilled artisans may be used.
  • the reactor comprises a dehydrating catalyst.
  • the conjugated alkenes may be produced using renewable resources.
  • a “renewable carbon” source refers to a carbon source that is made from modern carbon that can be regenerated within several months, years or decades rather than a carbon source derived from fossil fuels (e.g., petroleum) that takes typically a million years or more to regenerate.
  • the terms “renewable carbon” and “biobased carbon” are used interchangeably herein.
  • “Atmospheric carbon” refers to carbon atoms from carbon dioxide molecules that have been free in earth's atmosphere recently, e.g. in the most recent few decades.
  • conjugated hydrocarbon terpenes used in any one of the embodiments described herein can be made from microorganisms, including bioengineered microorganisms, using a renewable carbon source.
  • Myrcene, ocimene, farnesene, isodehydrosqualene, isosqualane precursor I, and isosqualane precursor II can be derived from a renewable carbon source using genetically modified microbial cells as described in U.S. Pat. No. 7,659,097, U.S. Pat. No. 7,399,323, International Patent Publication WO 2007/139924, International Patent Publication WO 2010/042208, or U.S. Patent Application Publication No.
  • olefinic feedstocks e.g. C 10 -C30 olefins
  • the olefinic feedstocks described herein can be used as substitutes for or as supplements to conventional olefinic feedstocks derived from fossil fuels.
  • renewable carbon content can be measured using any suitable method.
  • renewable carbon content can be measured according to ASTM D6866-1 1, "Standard Test Methods for Determining the Biobased Content of Solid, Liquid, and Gaseous Samples Using Radiocarbon Analysis,” published by ASTM International, which is incorporated herein by reference in its entirety.
  • Some carbon in atmospheric carbon dioxide is the radioactive 14 C isotope, having a half-life of about 5730 years.
  • Atmospheric carbon dioxide is utilized by plants to make organic molecules.
  • the atmospheric 14 C becomes part of biologically produced substances.
  • the biologically produced organic molecules degrade to produce carbon dioxide into the atmosphere, no net increase of carbon in the atmosphere is produced as a result, which may control or diminish undesired climate effects that may result when molecules produced from fossil fuels degrade to produce carbon dioxide to increase carbon in the atmosphere.
  • Isotope fractionation occurs during physical processes and chemical reactions, and is accounted for during radiocarbon measurements. Isotope fractionation results in enrichment of one isotope over another isotope. Exemplary processes that can affect isotope fractionation include diffusion (e.g., thermal diffusion), evaporation, and condensation. In some chemical reactions, certain isotopes may exhibit different equilibrium behaviors than others. In some chemical reactions, kinetic effects may affect isotope ratios. In the carbon cycle of plants, isotope fractionation occurs. During photosynthesis, the relative amounts of different carbon isotopes that are consumed are 12 0 13 0 14 C, due to slower processing of heavier isotopes.
  • the international reference standard for isotope fractionation between 13 C and 12 C is PDB (Pee Dee Belemnite standard) or VPDB (Vienna Pee Dee Belemnite standard, replacement for depleted PDB standard).
  • R(sample) 13 C/ 12 C
  • R(VPDB standard) 13 C/ 12 C for the VPDB standard.
  • 5 l3 C is the relative change of the 13 C/ 12 C ratio for a given sample from that of the VPDB standard.
  • Carbon isotopic ratios are reported on a scale defined by adopting a 5 U C value of +0.00195 for NBS- 19 limestone (RM 8544) relative to VPDB.
  • C content of a sample can be measured using any suitable method.
  • C content can be measured using Accelerator Mass Spectrometry (AMS), Isotope Ratio Mass Spectrometry (IRMS), Liquid Scintillation Counting (LSC), or a combination of two or more of the foregoing, using known instruments.
  • Activity refers to the number of decays measured per unit time and per unit mass units. To compare activity of a sample with that of a known reference material, isotope fractionation effects can be normalized.
  • a w A s ⁇ [( i3 C/ ⁇ C)reference]/[( i3 CrC)sample] ⁇ .
  • the factor 0.95 is used to correct the value to 1950 because by the late 1950s, 14 C in the atmosphere had artificially risen about 5% above natural values due to testing of thermonuclear weapons.
  • the AD 1950 standard had 100 pMC. Fresh plant material may exhibit a pMC value of about 107.5.
  • Biobased carbon content is determined by setting 100% biobased carbon equal to the pMC value of freshly grown plant material (such as corn), and pMC value of zero corresponds to a sample in which all of the carbon is derived from fossil fuel (e.g., petroleum).
  • a sample containing both modern carbon and carbon from fossil fuels will exhibit a biobased carbon content between 0 and 100%.
  • a sample that is more than several years old but containing all biobased carbon (such as wood from a mature tree trunk) will exhibit a pMC value to yield a biobased carbon content > 100%.
  • Renewable carbon content or biobased carbon content as used herein refers to fraction or percent modern carbon determined by measuring 14 C content, e.g., by any of Method A, Method B, or Method C as described in ASTM D6866- 1 1 "Standard Test Methods for Determining the Biobased Content of Solid, Liquid, and Gaseous Samples Using Radiocarbon Analysis.” Counts from 14 C in a sample can be compared directly or through secondary standards to SRM 4990C. A measurement of 0% 14 C relative to the appropriate standard indicates carbon originating entirely from fossils (e.g., petroleum based). A measurement of 100% 14 C indicates carbon originating entirely from modern sources. A measurement of >100% 14 C indicates the source of carbon has an age of more than several years.
  • the olefinic feedstocks described herein originate from renewable carbon sources.
  • the olefinic feedstocks have a 8 l3 C of from about - 1 1 to about -6 %o, from about - 15 to about - 10 %o, from about -22 to about - 15 %o, from about -22 to about -32 %o, from -8 to about - 18 %o, from about - 14 to about - 12 % 0 , or from about - 13 to about - 1 1 /oo.
  • the olefinic feedstocks have a f M greater than about 0.3, greater than about 0.4, greater than about 0.5, greater than about 0.6, greater than 0.7, greater than about 0.8, greater than about 0.9, or greater than about 1.0. In some variations, the olefinic feedstocks have a f M of about 1.0 to about 1.05, about 1.0 to about 1.1, or about 1.1 to about 1.2. In some variations, the olefinic feedstocks have a 8 l3 C from about -15 to about -10 %o and a f M greater than about 0.5, greater than about 0.7, or greater than about 1.0.
  • the olefinic feedstocks have a 8 l3 C from about -8 to about -18 %o and a f M greater than about 0.5, greater than about 0.7, or greater than about 1.0.
  • the conjugated hydrocarbon terpene e.g. , myrcene, ⁇ -farnesene, or a-farnesene
  • the renewable carbon content of the olefinic feedstocks may be measured using any suitable method, e.g., using radiocarbon analysis as described herein.
  • the olefinic feedstocks described herein comprise virtually no sulfur and no aromatic compounds, making them environmentally preferable over conventional olefins derived from fossil fuels, which in many cases contain sulfur and aromatics, such as naphthalenes.
  • the olefinic feedstocks comprise less than about 10 ppm sulfur, less than about 1 ppm sulfur, less than about 100 ppb sulfur, less than about 10 ppb sulfur or less than about 1 ppb sulfur.
  • the olefinic feedstocks comprise less than about 10 ppm aromatics, less than about 1 ppm aromatics, less than about 100 ppb aromatics, less than about 10 ppb aromatics or less than about 1 ppb aromatics.
  • the olefinic feedstocks comprise less than about 10 ppm sulfur and less than about 10 ppm aromatics, less than about 1 ppm sulfur and less than about 1 ppm aromatics, less than about 100 ppb sulfur and less than about 100 ppb aromatics, less than about 10 ppb sulfur and less than about 10 ppb aromatics, or less than about 1 ppb sulfur and less than about 1 ppb aromatics.
  • the olefinic feedstocks are derived from an acyclic conjugated hydrocarbon alkene
  • the olefinic feedstocks described herein may comprise less than about 5%, less than about 2%, less than about 1%, less than about 0.1%, or less than about 0.01% cyclic compounds.
  • the olefinic feedstocks described herein comprise one or more methylated alkenes, e.g. , one or more methylated mono-alkenes, methylated di-alkenes, methylated tri- alkenes, or methylated tetra-alkenes, where the number of carbon atoms in the base alkene for any of the above corresponds to the number of carbon atoms in the main chain of a conjugated alkene (which may be a hydrocarbon terpene in some variations) used to make the feedstock, and the number of methyl substituents corresponds to the number of methyl substituents (or in some cases, methyl and methylene substituents) on the conjugated alkene (which may be a hydrocarbon terpene in some variations) used to make the feedstock.
  • methylated alkenes e.g. , one or more methylated mono-alkenes, methylated di-alkenes, methylated tri- alken
  • the olefinic feedstocks are derived from a Cio-C 30 conjugated alkene comprising 1-10 methyl or methylene substituents, e.g., 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 methyl or methylene substituents.
  • the olefinic feedstocks are derived from a C10-C30 conjugated alkene comprising at least one ethyl or vinyl substituent.
  • the olefinic feedstocks are derived from a C 10 -C30 conjugated alkene comprising 1-10 methyl or methylene substituents and at least one ethyl or vinyl substituent.
  • the olefinic feedstocks described herein can comprise a well-defined distribution of methylated alkenes and (in some cases methylated alkanes) within a very narrow molecular weight range (e.g. a distribution spanning a range from about 2-10 amu, or from about 2-20 amu) as molecules within the distribution have the same number of carbon atoms.
  • a feedstock comprising a very narrow molecular weight range can be produced directly, without the need for cracking or a separation process such as distilling from a crude mixture, as is commonly employed in the production of C 10 -C30 olefinic feedstocks from petroleum products.
  • An olefinic feedstock described herein that is derived from more than one partially hydrocarbon terpene species can exhibit a broader but predictable molecular weight distribution as produced, again without the need for a separation process.
  • the feedstocks described herein can provide unique methylated olefinic feedstocks that do not require an extra alkylation step to incorporate short chain branching, or any separation step to isolate. Furthermore, the degree of branching, the type of branching, and the branching position in the olefins in feedstocks described herein are predetermined by the source hydrocarbon terpene or terpenes, unlike other feedstocks comprising branched olefins, wherein the branched olefins comprise a complex mixture of isomers wherein the degree of branching, the type of branching and the branching position are all varied.
  • olefinic feedstocks from a conjugated alkene (e.g., a C 10 -C30 conjugated hydrocarbon terpene) comprising at least one conjugated diene and at least one additional carbon-carbon double bond by controlled partial hydrogenation.
  • a conjugated alkene e.g., a C 10 -C30 conjugated hydrocarbon terpene
  • an olefinic feedstock is made by controlled partial hydrogenation of myrcene, ocimene, farnesene, springene, geranylfarnesene, isodehydrosqualene, isosqualane precursor I, or isosqualane precursor II.
  • the controlled partial hydrogenation process may in some variations be staged, so as to comprise two or more stages, with each stage designed to tune the resulting olefin composition of the olefinic feedstock.
  • a multi-stage hydrogenation process may be used to produce an olefinic feedstock that is rich in mono-olefinic species (e.g., comprises at least about 60% mono-olefins).
  • a first hydrogenation stage may comprise selectively hydrogenating at least one olefinic bond in the conjugated diene to produce an intermediate partially hydrogenated product
  • a second hydrogenation stage may comprise selectively hydrogenating the intermediate product in a second hydrogenation stage to produce a desired olefinic composition, e.g. , an olefinic composition rich in mono-olefins, and/or an olefinic composition in which alkane formation has been minimized.
  • compositions for olefinic feedstocks derived by partial hydrogenation of conjugated hydrocarbon terpenes are disclosed herein: i) olefinic feedstocks compositions that have very low amounts of conjugated dienes (e.g., less than about 10% conjugated diene, less than about 5% conjugated diene, or less than about 1% conjugated diene); ii) olefmic feedstocks comprised predominantly of mono- olefins and di-olefins (e.g., at least about 80%, or at least about 90%, or at least about 95% mono-olefins and di-olefins); iii) olefmic feedstock compositions comprised predominantly of mono-olefinic species (e.g., at least about 60%, at least about 65%, at least about 70%, at least about 75%, or at least about 80% mono
  • di-olefins that are present may be substantially unconjugated, e.g., so that a composition comprises at most about 2%, at most about 1%, at most about 0.5%, at most about 0.1%, or no detectable conjugated species.
  • alpha-olefins derived from a 1,3-diene conjugated hydrocarbon terpene e.g., a C 10 -C30 conjugated hydrocarbon terpene such as farnesene, myrcene, ocimene, springene, or
  • conjugated alkene e.g., a conjugated hydrocarbon terpene, which may be an acyclic or cyclic Cio-C 30 conjugated hydrocarbon terpene
  • a conjugated alkene e.g., a conjugated hydrocarbon terpene, which may be an acyclic or cyclic Cio-C 30 conjugated hydrocarbon terpene
  • controlled (e.g., staged) partial hydrogenation e.g., staged
  • a conjugated alkene comprising at least one conjugated diene and at least one additional C-C double bond is represented by structure Al (or a stereoisomer thereof, including ( ⁇ , ⁇ ), ( ⁇ , ⁇ ), (Z,E), and (Z,Z) stereoisomers and rotational isomers):
  • R 1 , R 2 , R 3 , R 4 , R 5 , and R 6 are each independently H, or a C 1 -C25 linear or branched, cyclic or acylic, saturated or unsaturated hydrocarbon group, and at least one of the group consisting of R 1 , R 2 , R 3 , R 4 , R 5 , and R 6 contains at least one carbon carbon double bond. In some variations at least one of R 1 , R 2 , R 3 , R 4 , R 5 , and R 6 may contain two, three, four, five, or six or more carbon carbon double bonds.
  • At least one of R 1 , R 2 , R 3 , R 4 , R 3 , and R 6 is a monoene substituted with one or more methyl roups or a polyene substituted with one or more methyl groups (e.g. ,
  • the conjugated alkene comprises a terminal carbon-carbon double bond as part of the conjugated diene and at least one additional carbon-carbon double bond, and has structure A3 (or a stereoisomer thereof including ( ⁇ , ⁇ ), ( ⁇ , ⁇ ), (Z,E), and (Z,Z) stereoisomers and rotational isomers):
  • R 1 , R 2 , R 3 , and R 4 are each independently H, or a C 1 -C25 linear or branched, cyclic or acyclic, saturated or unsaturated hydrocarbon group, and at least one of the group consisting of R 1 , R 2 , R 3 , and R 4 contains at least one carbon carbon double bond.
  • at least one of R 1 , R 2 , R 3 , and R 4 may contain two, three, four, five, or six or more carbon carbon double bonds.
  • at least one 1, R 2 , R 3 , and R 4 is a monoene substituted with one or more meth l groups or a polyene substituted or
  • the conjugated alkene has structure A5 (or a stereoisomer thereof):
  • R 1 , R 2 and R 3 are each independently H or a C 1 -C25 linear or branched, cyclic or acyclic, saturated or unsaturated hydrocarbon group, and at least one of the group consisting of R 1 , R 2 and R 3 contains at least one carbon carbon double bond. In some variations, at least one of R 1 , R 2 and R 3 may contain two, three, four, five, or six or more carbon carbon double bonds. In some variations, at least one of R 1 , R 2 and R 3 is a ubstituted with one or more methyl
  • the conjugated alkene has structure A7 (or a stereoisomer thereof including ( ⁇ , ⁇ ), ( ⁇ , ⁇ ), (Z,E), and (Z,Z) stereoisomers and rotational isomers):
  • R 1 and R 3 are each independently H or a C1-C25 linear or branched, cyclic or acyclic, saturated or unsaturated hydrocarbon group, and at least one of the group consisting of R 1 and R 3 contains at least one carbon carbon double bond. In some variations, at least one of R 1 and R 3 may contain two, three, four, five, or six or more C-C double bonds. In some variations, at least one of R 1 and R 3 is a monoene substituted with one or more meth l groups, or a polyene substituted with one or more methyl groups (e.g.,
  • the conjugated alkene has structure A9 (or a stereoisomer thereof including ( ⁇ , ⁇ ), ( ⁇ , ⁇ ), (Z,E), and (Z,Z) stereoisomers and rotational isomers):
  • R is a C5-C25 linear or branched, cyclic or acyclic unsaturated hydrocarbon group containing at least one carbon carbon double bond, or in some variations two, three, four, five, or six or more carbon carbon double bonds.
  • at R 3 is a monoene substituted with one or more methyl groups
  • a conjugated alkene comprising at least one additional carbon-carbon double bond from which the olefinic feedstock is derived is a conjugated hydrocarbon terpene comprising at least one additional carbon-carbon double bond.
  • a conjugated hydrocarbon terpene having any of the above-listed structures A1-A9 (or stereoisomers thereof) may be used to make the olefinic feedstocks described herein.
  • a conjugated hydrocarbon terpene having structure A9 with R 3 being a C5-C25 monoene or polyene may be used to make the olefinic feedstocks described herein.
  • a conjugated hydrocarbon terpene comprising at least one conjugated diene and at least one additional carbon carbon double bond by controlled hydrogenation comprise selectively hydrogenating at least one olefmic bond in the conjugated diene in a first stage to produce a partially hydrogenated olefmic intermediate, and selectively hydrogenating the partially hydrogenated olefmic intermediate in one or more subsequent stages (e.g. a second stage for a two stage process) to produce the olefmic feedstock having a desired composition.
  • a conjugated hydrocarbon terpene comprising at least one conjugated diene and at least one additional carbon carbon double bond by controlled hydrogenation comprise selectively hydrogenating at least one olefmic bond in the conjugated diene in a first stage to produce a partially hydrogenated olefmic intermediate, and selectively hydrogenating the partially hydrogenated olefmic intermediate in one or more subsequent stages (e.g. a second stage for a two stage process) to produce the olefmic feedstock having a desired composition.
  • staged partial hydrogenation methods may be applied to any of the aforementioned conjugated alkenes having structures A1-A9 to produce an olefmic feedstock, including but not limited to C10-C30 conjugated hydrocarbon terpenes such as myrcene, ocimene, farnesene, springene, geranylfamesene, isodehydrosqualene, isosqualane precursor I, and isosqualane precursor II.
  • an olefmic feedstock is produced by staged partial hydrogenation from a conjugated hydrocarbon terpene produced by a bioengineered microorganism using a renewable carbon source.
  • the staged partial hydrogenation is conducted in two stages. In some variations, the staged partial hydrogenation is conducted in three or more stages.
  • methods comprising selectively hydrogenating a conjugated terpene comprising at least three olefmic bonds wherein two of the at least three olefmic bonds form a conjugated diene to make a composition rich in mono-olefins and comprising a limited amount of di-olefins.
  • no substantial quantities of conjugated di-olefins are present.
  • Such methods may be utilized when a mono-olefinic feedstock is desired, and the presence of di-olefins causes undesired side reactions, cross-products and the like.
  • the methods may be capable of making a composition comprising at least about 50% mono-olefinic species and at most about 10% di-olefmic species, comprising at least about 50% mono-olefinic species and at most about 10% di-olefmic species, at least about 50% mono-olefinic species and at most about 10% di-olefmic species, at least about 50% mono- olefinic species and at most about 5% di-olefmic species, at least about 50% mono-olefmic species and at most about 3% di-olefmic species, at least about 50% mono-olefmic species and at most about 1% di- olefmic species, at least about 50% mono-olefmic species and at most about 0.5% di-olefmic species, at least about 55% mono-olefmic species and at most about 10% di-olefmic species, at least about 55% mono-olefmic species and at most about 5% di-olefmic species, at least about 55% mono-olefmic species and at most
  • the amount of sulfur may be less than about lppm.
  • the amount of aromatic compounds may be less than about lppm.
  • the amount of sulfur and the amount of aromatic compounds may each be less than lppm.
  • the terpene is microbially derived from renewable carbon sources, and has a renewable carbon content of about 100%.
  • a model stepwise or staged hydrogenation process can be described as follows using farnesene as a model compound.
  • the tetraene is reduced to a triene in a first hydrogenation stage having a first rate constant k[l ]; the triene is reduced to a diene in a second hydrogenation stage having a second rate constant k[2]; the diene is reduced to a monoene in a third hydrogenation stage having a third rate constant k[3]; and the monoene is reduced to an alkane in a fourth hydrogenation stage having a fourth rate constant k[4].
  • the stepwise hydrogenation process can be described as follows: k[l] k[2] k[3] k[4] farnesene ⁇ tri-olefin ⁇ di-olefin ⁇ mono-olefin ⁇ farnesane
  • k[3] may be at least about two times, at least about three times, at least about five times, or at least about ten times k[4].
  • k[l ] :k[2] may be at least about 10: 1 , e.g., about 10: 1 , 20: 1 , 30: 1 , 40: 1 , 50: 1 , 60: 1 , 70: 1 , 80: 1 , 90: 1 , 100: 1 , 200: 1 , or even higher.
  • k[2] may be similar to k[3], e.g., a ratio k[2] :k[3] may be about 1 : 1 , 2: 1, or 1 :2.
  • a ratio k[l ] :k[4] may be at least about 20: 1 , e.g., about 20: 1 , 30: 1 , 40: 1 , 50: 1 , 60: 1 , 70: 1 , 80: 1 , 90: 1, 100: 1 , 200: 1 , or even higher.
  • k[l ] :k[2] :k[3] :k[4] may be about 80: 10:5: 1.
  • k[l ] :k[2] :k[3] :k[4] may about 80: 10:5:0.5 or 80: 10:5:0.25.
  • reaction conditions may be selected such that the ratio k[3] :k[4] results a final olefmic feedstock in which the mono-olefinic content is at least about 60%, at least about 65%, at least about 70%, at least about 75%, or at least about 80%, the di-olefinic content is about 12% or less, about 10% or less, about 8% or less, about 5% or less, or less than 5%, and the alkane content is about 25% or less, about 20% or less, about 18% or less, about 15% or less, about 10% or less, or about 8% or less.
  • the ratio k[3]:k[4] can be tuned using staged hydrogenation processes described herein to tune relative populations of mono-olefinic, di-olefinic, and alkane in an olefmic feedstock.
  • the conjugated diene is selectively hydrogenated in the first stage.
  • hydrogenation in a subsequent stage or stages is controlled to form unconjugated polyenes (e.g., di-olefins) and to selectively favor hydrogenation of the unconjugated polyene (e.g., di-olefins) over hydrogenation of mono-olefin.
  • unconjugated polyenes e.g., di-olefins
  • the di-olefin population increases, reaches a peak after about two equivalents of hydrogen have been added, and then
  • the concentration of mono-olefin monotonically decreases.
  • the concentration of mono-olefin monotonically increases as until about three equivalents of hydrogen have been added, and subsequently begins to decrease as more saturated hydrocarbon is formed.
  • the degree of hydrogenation can be carefully controlled to achieve a composition in which mono-olefin content is maximized while di-olefin is minimized, to achieve a composition in which mono-olefin content is maximized while alkane is minimized, or to achieve a composition in which mono-olefin content is maximized by di-olefin and alkane are minimized.
  • the catalysis conditions are changed following a first hydrogenation stage.
  • the catalysis conditions include amount of hydrogen, catalyst, catalyst loading, temperature, hydrogen pressure, and reaction time, and any one of or any combination of each of these variables may be independently varied between the first and subsequent (e.g. second) hydrogenation stages.
  • catalysis conditions of a final (e.g., second stage in a two stage process) stage are selected to favor hydrogenation of polyene species present in an intermediate product over hydrogenation of mono-olefinic species in the intermediate product, thereby limiting the quantity of alkane produced in the final olefinic feedstock and reducing concentration of polyene species.
  • the presence of polyene species in a mono-olefinic feedstock may lead to undesired side reactions and cross-products in some reactions.
  • the amount of hydrogen delivered, the catalyst, catalyst loading, and reaction conditions (reaction temperature, hydrogen pressure and time) in a first stage are selected so that less than about 10%, less than about 5%, less than about 3%, less than about 1%, less than about 0.3% (or even fewer) of the molecules in the intermediate product have a conjugated diene moeity after the first hydrogenation stage.
  • the catalyst type (and associated catalysis conditions) for the first stage are selected to be those that are known in the art to be selective for hydrogenating conjugated diene moieties and are active at temperatures below which thermal dimerization, cyclization, isomerization, or other competing or degradation process of the conjugated alkene occurs.
  • a catalyst system that is active at a temperature in a range from about 20°C to about 1 10°C may be used to catalyze hydrogenation of ⁇ -farnesene for a first stage to reduce probability that such a competing process occurs.
  • palladium catalysts e.g., palladium catalysts prepared via reduction by organoaluminum compounds of Pd(II) complexes (e.g., PdC3 ⁇ 4) with nitrogen-containing ligands;
  • ruthenium compounds, rhodium compounds, chromium compounds, iridium compounds; and cobalt compounds may be selected as a catalyst for a first stage in which the conjugated diene is selectively reduced.
  • regioselective hydrogenation catalysts for 1,3-dienes are provided in Jong Tae Lee et al, "Regioselective hydrogenation of conjugated dienes catalyzed by hydridopentacyanocobaltate anion using ⁇ -cyclodextrin as the phase transfer agent and lanthanide halides as promoters," J.
  • a metal catalyst such as palladium, platinum, nickel, copper, copper- chromium, rhodium, ruthenium or molybdenum on on various supports may be used in the first and/or second stage.
  • palladium-containing catalysts that can be used in the first and/or second hydrogenation stage are Pd/C, Pd/Al 2 0 3 , Pd/titanium silicate, Pu7Si0 2 , Pd on titania, Pd on zirconia, and Pd on alumina-silica).
  • catalysis conditions may be selected to be relatively mild in the first stage, e.g., lower activity catalyst, lower catalyst loading, and/or lower temperature (e.g., temperature of 110°C or lower, or 100°C or lower) to allow selective hydrogenation of at least one olefinic bond in the conjugated diene over other olefinic bonds that are present, without undesired levels of thermal dimerization, isomerization, or oligomerization.
  • a catalyst used in the first and/or subsequent stage is activated before use. For example, some copper-containing catalysts (e.g., Cu/Si0 2 or a Cu-Cr catalyst) is activated before use (e.g., at 150-180°C).
  • catalysts that require activation at high temperatures are used in second or subsequent stages of hydrogenation to avoid exposure of the conjugated terpene to temperatures which may cause dimerization and the like. In some variations, more active catalysis conditions are selected for the second second or subsequent stages.
  • the intermediate product produced after the first stage contains limited amounts of conjugated diene (e.g., less than about 10%) and limited amounts of alkane (e.g., less than about 1%), the intermediate product consists essentially of unconjugated polyenes in which the number of olefinic bonds is one less than in the starting conjugated alkene.
  • Examples 8 and 9 herein provide non-limiting examples of a first stage of partial hydrogenation of ⁇ -farnesene in which one molar equivalent of hydrogen was consumed and the resulting olefmic mixture consists essentially of tri-olefinic species.
  • Examples 16-32 herein provide non- limiting examples of a hydrogenation process in which about 1-1.5 equivalents of hydrogen are consumed in a first hydrogenation stage.
  • the intermediate product produced after the first stage contains limited amounts of conjugated diene (e.g., less than about 10%) and limited amounts of alkane (e.g., less than about 2%), the intermediate product consists essentially of a mixture of monoenes and unconjugated polyenes.
  • Certain Examples herein provide non-limiting examples of partial hydrogenation of ⁇ -farnesene in which about 2.5 molar equivalents of hydrogen were consumed and the resulting olefmic mixture consists essentially of monoenes and unconjugated dienes, with less than about 10% trienes, and no detectable amount of alkane or conjugated diene.
  • the amount of hydrogen, catalyst, catalyst loading, and reaction conditions can be independently varied in the second stage relative to the first stage to partially hydrogenate the olefmic intermediate product to produce a desired olefmic feedstock.
  • reaction temperature, hydrogen pressure and time can be independently varied in the second stage relative to the first stage to partially hydrogenate the olefmic intermediate product to produce a desired olefmic feedstock.
  • the catalyst and catalysis conditions in the second stage may be selected to preferentially hydrogenate unconjugated polyenes over monoenes.
  • hydrogen pressure and temperature are reduced in the second stage so as to favor hydrogenation of unconjguated polyenes over monoenes.
  • staged hydrogenation processes for a conjugated hydrocarbon terpene comprising at least one additional olefmic bond may include three or more distinct hydrogenation stages
  • a two stage hydrogenation process is used to produce an olefmic feedstock.
  • catalysis conditions are such that at least one olefmic bond in the conjugated diene moiety is preferentially hydrogenated and sufficient hydrogen is delivered (e.g., at least about 1-1.5 molar equivalent of hydrogen, or in some cases about 2-2.5 molar equivalents of hydrogen) so that the quantity of conjugated diene remaining is low, e.g.
  • Hydrogenation conditions in the first stage may be relatively mild (e.g. , temperature is in a range from about 40°C to about 110°C) so that essentially no alkane is formed and essentially no competing reactions (e.g., thermal dimerization, cyclization, isomerization, and the like) occur.
  • about one molar equivalent of hydrogen is consumed and catalyst and catalyst conditions are selected so that the intermediate olefmic product produced after the first stage consists essentially of unconjugated polyenes (e.g. , unconjugated trienes in the case of farnesene).
  • the amount of hydrogen, catalyst and catalysis conditions are selected so that the intermediate product produced after the first stage consists predominantly of monoenes and unconjugated polyenes (monoenes and unconjugated dienes in the case of farnesene), e.g., at least about 80%, at least about 85%, at least about 90%, at least about 95% unconjugated polyenes, with little or no alkane and little or no conjugated diene.
  • the amount of hydrogen, the catalyst and the catalysis conditions may be selected based on the intermediate distribution of species formed in the first stage to produce a desired final distribution of species.
  • catalysis conditions of the second stage may be tuned to selectively hydrogenate the unconjugated polyenes rather than the mono-olefins so as to produce a feedstock consisting of predominantly mono-olefins, e.g.
  • Certain Examples herein provide nonlimiting examples of two-stage partial hydrogenations of ⁇ -farnesene to produce mono-olefinic feedstocks.
  • the temperature of a first hydrogenation stage of a conjugated hydrocarbon terpene may be kept low (e.g., kept below about below about 120°C, below about 100°C, or below about 80°C, below about 50°C, or below about 40°C) to preferentially hydrogenate at least one olefinic bond in the conjugated diene moiety over other olefinic bonds and to reduce occurrence of competing processes (e.g. , thermal dimerization, cyclization, isomerization, and the like).
  • catalysis conditions for a second stage may be selected to preferentially hydrogenate unconjugated polyenes (e.g., di-olefins and tri-olefins in the case of farnesene) over mono-olefins, without creating undesired amounts of completely saturated alkane.
  • a second hydrogenation stage may be conducted at a higher temperature (e.g.
  • the conjugated diene moiety has been eliminated or reduced to a very low concentration by the first stage, probability of thermal dimerization or other competing reactions associated with the conjugated diene are greatly reduced, even at higher temperatures.
  • the catalyst and catalyst loading are kept constant between the first and second stages, but the temperature is increased in the second stage relative to the first stage, e.g., as described here.
  • a metal catalyst such as palladium, platinum, nickel, copper, copper- chromium, rhodium, ruthenium or molybdenum on on various supports may be used in the second or subsequent hydrogenation stages.
  • palladium-containing catalysts that can be used in the second hydrogenation stage are Pd/C, Pd/Al 2 0 3 , Pd/titanium silicate, Pd/Si0 2 , Pd on titania, Pd on zirconia, and Pd on alumina- silica.
  • a catalyst used in a second or subsequent stage is activated before use.
  • some copper-containing catalysts e.g., CU/S1O 2 or a Cu-Cr catalyst
  • a metal catalyst known in the art for preferentially hydrogenating di-olefins or higher polyenes over mono-olefins is used in the second or subsequent stages.
  • reaction conditions in latter hydrogenation stage are selected to favor dehydrogenation of paraffins. For example, temperature is increased and hydrogen pressure is reduced in a final hydrogenation stage so as to favor dehydrogenation of paraffins, without formation of undesired side products.
  • a second hydrogenation stage may be conducted at a lower hydrogen pressure (e.g., a second stage hydrogen pressure of about 10- 100 psig, such as about 10, 20, 30, 40, 50, 60, 70, 80, 90 or 100 psig) than the hydrogen pressure of a first stage to favor hydrogenation of unconjugated polyenes (e.g., di-olefins and tri-olefins in the case of farnesene) over mono-olefins.
  • the hydrogen pressure in the second stage is below 50 psig, e.g., about 10, 20, 30, or 40 psig.
  • a second hydrogenation stage may be conducted at a higher temperature (e.g., at least about 50°C, 100°C, or 150°C higher than a first hydrogenation stage) and at a lower hydrogen pressure (e.g. at a pressure that is 10-990 psig lower than pressure in a first stage).
  • the catalyst and catalyst loading are kept constant between the first and second stages, but the temperature is increased in the second stage relative to the first stage and the hydrogen pressure is lowered in the second stage relative to the first stage, e.g., as described here.
  • the temperature of the first stage is in a range from about 40°C to about 160°C and the hydrogen pressure in the first stage is in a range from about 100 psig to about 1000 psig
  • the temperature in the second stage is in a range from about 120°C to about 260°C and the hydrogen pressure in the second stage is in a range from about 10 psig to about 100 psig.
  • a staged partial hydrogenation process includes more than two temperature stages, e.g., three, four, five, or more temperature regimes.
  • a first temperature stage involves no external heating, and self-heat is provided by the exotherm of the hydrogenation reaction.
  • a staged partial hydrogenation process includes a first self-heated stage during which about 0.5 equivalents or less of hydrogen is added (e.g., about 0.3-0.5 equivalents of hydrogen), followed by a second temperature stage during which the temperature is raised (e.g., to about 80-1 10°C, such as about 80°C, 90°C, 100°C, or 1 10°C) and the total hydrogen equivalents added is raised to about 1.5 (e.g., additional 1-1.2 equivalents), followed by a third stage during which an additional 1.5 equivalents hydrogen is added and the temperature is raised to about 160-240°C, e.g., about 160°C, 170°C, 180°C, 190°C, 200°C, 210°C, 220°C, 230°C, or 240°C).
  • the hydrogen pressure is maintained at a relatively constant pressure (e.g., a pressure of about 50-200 psig, such as about 50, 100, 150 or 200 psig) throughout all three stages.
  • the hydrogen pressure is maintained (e.g., at about 50-200 psig for the first self-heating stage and the second stage (e.g., a pressure of about 50-200 psig, such as about50, 100, 150 or 200 psig), and the hydrogen pressure is reduced during the third stage to a pressure less than about 50 psig (e.g., about 5, 10, 15, 20, 25, 30, 35, or 40 psig).
  • a staged hydrogenation process comprises a first self-heat stage during which about 0.5 equivalents or less of hydrogen is added (e.g., about 0.3-0.5 equivalents), a second stage during which about 1 - 1.2 equivalents of hydrogen is added and the temperature is about 100°C, and a third stage during which about 1.5 equivalents of hydrogen is added and the temperature is about 160°C, where the hydrogen pressure is not varied (e.g., held at about 50 psig, 100 psig, 150 psig, or 200 psig). In one variant, the hydrogen pressure is about 100 psig throughout the hydrogenation process.
  • a staged hydrogenation process comprises a first self-heat stage during which about 0.5 equivalents or less of hydrogen is added (e.g., about 0.3-0.5 equivalents) and the hydrogen pressure is about 50-200 psig (e.g., about 50, 100, 150, or 200 psig), a second stage during which about 1 - 1.2 equivalents of hydrogen is added and the temperature is about 100°C and the hydrogen pressure is maintained as in the self-heat stage, and a third stage during which the temperature is increased to about 160-240°C (e.g., about 160°C, 170°C, 180°C, 190°C, 200°C, 210°C, 220°C, 230°C or 240°C) and the hydrogen pressure is decreased to a pressure less than about 50 psig (e.g., about 5, 10, 15, 20, 25, 30, 35, or 40 psig).
  • the pressure in the first self- heat stage and the second stage is about 100 psig
  • Nonlimiting examples of temperature and hydrogen pressure hydrogenation conditions for a first hydrogenation stage in which about 1 -2.5 (e.g., about 1 - 1.5, or about 2-2.5) equivalents of hydrogen are consumed to selectively hydrogenate the conjugated diene are provided in Table 1A. It should be noted that the first hydrogenation stage may or may not be preceded by a self-heated hydrogenation stage as described above.
  • Each "X" in Table 1A discloses reaction conditions comprising the temperature indicated in the column heading and the hydrogen pressure indicated in the row headings.
  • Nonlimiting examples of catalysts that may be used together with the temperatures and hydrogen pressure combinations indicated in Table 1A include Pd/C (e.g., 5- 10wt% Pd), Pd/Al 2 0 3 (e.g., 0.2-0.6wt% Pd), Pd/Si0 2 (e.g., 0.2- 0.6 wt% Pd), and Lindlar's catalyst.
  • Pd/C e.g., 5- 10wt% Pd
  • Pd/Al 2 0 3 e.g., 0.2-0.6wt% Pd
  • Pd/Si0 2 e.g., 0.2- 0.6 wt% Pd
  • Lindlar's catalyst e.g., 0.2- 0.6 wt% Pd
  • Nonlimiting examples of hydrogenation conditions for a second hydrogenation stage after about 1-2.5 (e.g., about 1-1.5, or about 2-2.5) equivalents of hydrogen have already been consumed by the conjugated alkene are provided in Table IB.
  • Each "X" in Table IB discloses reaction conditions comprising the temperature indicated in the column heading and the hydrogen pressure indicated in the row headings.
  • Nonlimiting examples of catalysts that may be used together with the temperatures and hydrogen pressure combinations indicated in Table IB include catalysts comprising Pt, Pd, Ni, Cu, Rh, Ru, and Mo on various supports, such as Pd/C (e.g., 5-10wt% Pd), Pd/Al 2 0 3 (e.g., 0.2-0.6wt% Pd), Pd/Si0 2 (e.g., 0.2-0.6 wt% Pd), Cu-based catalyst (e.g., Cu/Si02), zeolites impregnated or exchanged with noble metals (e.g., Pd or Pt), and Pt(S)/C.
  • Pd/C e.g., 5-10wt% Pd
  • Pd/Al 2 0 3 e.g., 0.2-0.6wt% Pd
  • Pd/Si0 2 e.g., 0.2-0.6 wt% Pd
  • Cu-based catalyst e.g., Cu/S
  • the catalyst used for a second hydrogenation stage after about 1-2.5 equivalents of hydrogen have been consumed by the conjugated alkene is 0.3 wt% Pd/Al 2 0 3 , and the temperature is about 200-210°C and the hydrogen pressure is about 1 bar (14 psi).
  • an inert gas such as dry nitrogen may be added to the reactor to increase the overall pressure while achieving a desired partial pressure of hydrogen.
  • a hydrogenation process may comprise any combination of first stage temperature and hydrogen pressure conditions disclosed in Table 1 A with second stage temperature and hydrogen pressure conditions described in Table IB, with the proviso that the combination selected yields the desired selectivity, yield and reaction time.
  • the temperature in the second stage is higher than in the first stage.
  • the hydrogen pressure is lower in the second stage than in the first stage.
  • the temperature is higher and the hydrogen pressure is lower in the second stage relative to the first stage.
  • reaction temperature in a second or subsequent stage may be increased by about 50-150°C, e.g., by about 50°C, by about 60°C, by about 70°C, by about 80°C, by about 90°C, by about 100°C, by about 1 10°C, by about 120°C, by about 130°C, by about 140°C, or by about 150°C.
  • hydrogen pressure is decreased so as to favor the reaction of di-olefin to form mono- olefin (k[3]) over the reaction of mono-olefin to form saturated hydrocarbon (k[4]).
  • reducing hydrogen pressure in the reactor limits the availability of hydrogen, which leads to favoring the reaction of di-olefin to form mono-olefin over the reaction of mono-olefin to form saturated hydrocarbon.
  • the hydrogen pressure in a second or subsequent stage may be decreased by about 50-100 psig, e.g., by about 50 psig, about 60 psig, about 70 psig, about 80 psig, about 90 psig, or about 100 psig.
  • temperature is increased and hydrogen pressure is decreased so as to favor the reaction of di-olefin to form mono-olefin (k[3]) over the reaction of mono-olefin to form saturated hydrocarbon (k[4]).
  • the reaction temperature in a second or subsequent stage may be increased by about 50-150°C (e.g., by about 50°C, about 60°C, about 70°C, about 80°C, about 90°C, about 100°C, about 120°C, or about 150°C), and the hydrogen pressure in a second or subsequent stage may be decrease by about 50-100 psig (e.g., decreased by about 50 psig, about 60 psig, about 70 psig, about 80 psig, about 90 psig, or about 100 psig).
  • the degree of hydrogenation to produce a mono-olefinic hydrocarbon terpene is adjusted to be about one hydrogen equivalent less than total hydrogenation (e.g., 75% hydrogenated for farnesene)
  • the degree of hydrdogenation is fine tuned to achieve a desired balance between mono-olefinic content, di-olefinic content and alkane content.
  • a desired balance is achieved when the degree of hydrogenation is slightly less than about one hydrogen equivalent less than total hydrogenation (e.g., slightly less than 75% for farnesene).
  • the hydrogenation degree at which mono-olefin is maximum occurs with a total degree of hydrogenation that is about 75% or slightly higher than 75%, and at a point at which alkane content has started to rise.
  • the degree of hydrogenation at which olefin content is maximized while both alkane and di-olefin content are minimized occurs at a degree of hydrogenation that is slightly lower than 75%, e.g., at about 70-74.5%, or about 70%, 70.5%, 71%, 72%, 72.5%, 73%, 73.5%, 74%, or 74.5% hydrogenated.
  • hydrogenation conditions are adjusted so that the mono-olefin: di-olefin ratio is about 10: 1 or greater, about 20: 1 or greater, about 30: 1 or greater, about 40: 1 or greater, about 50: 1 or greater, about 60: 1 or greater, about 70: 1 or greater, about 80: 1 or greater, about 90: 1 or greater, about 100: 1 or greater, about 120: 1 or greater, about 140: 1 or greater, about 160: 1 or greater, about 180: 1 or greater, about 200: 1 or greater, about 220: 1 or greater, about 240: 1 or greater, about 260: 1 or greater, about 280: 1 or greater, about 300: 1 or greater, about 320: 1 or greater, about 340: 1 or greater, about 360: 1 or greater, about 380: 1 or greater, about 400: 1 or greater, about 500: 1 or greater, about 1000: 1 or greater, or even greater.
  • staged partial hydrogenation may be used to carry out the methods described herein.
  • the catalysis conditions structure of catalyst, type of catalyst, catalyst loading, reaction time, temperature and/or hydrogen pressure
  • the hydrogenation may be conducted in a single reactor such that the catalyst is not changed between stages.
  • the hydrogenation may be conducted in one or more serial reactors so that the catalyst used in different stages may be different. If a single reactor is used for a multi-stage hydrogenation, a batch reactor (e.g., batch slurry reactor) or fixed bed or flow through type reactor may be used. If a batch reactor is used, any suitable type of batch reactor may be used, e.g., a batch slurry reactor.
  • any suitable type of fixed bed or flow through type reactor may be used.
  • efficient heat transfer to the hydrocarbon terpene and residence time in certain temperature zones are important for effective staged hydrogenation reaction to achieve desired selective hydrogenation as described herein.
  • the reactor operates safely while removing exothermic heat due to the hydrogenation, and while controlling temperature in the desired ranges.
  • diameters of fixed bed reactors are limited to allow control of the exotherm and overall temperature control of the reactor. It is desired to tune reaction conditions to avoid formation of thermal dimers. Temperature in a first stage is limited to avoid formation of thermal dimers. Further, dilution by a diluent may be used limit formation of thermal dimers.
  • Thermal dimer formation is second order with respect to terpene concentration, whereas hydrogenation rates are typically between zero order and first order with respect to the terpene, so that dilution by a diluent generally increases the ratio of hydrogenation rate to dimerization rate.
  • Any suitable dilution is used, e.g., about 1 : 100, 1 :50, 1 :20, 1 : 10, 1 :5, 1 :4, 1 :3, 1 :2, 1 : 1, 2: 1, 3: 1, 4: 1, 5: 1, or 10: 1 terpene: diluent.
  • the terpene is diluted about 25% in a diluent.
  • the hydrocarbon terpene is carried through the flow reactor in a liquid diluent to provide heat transfer between reactor walls and the terpene.
  • the liquid diluent is selected to consume no hydrogen, to be inert under the reaction conditions, and to provide efficient thermal transfer between the terpene substrate and the source of heat in the reactor.
  • a suitable liquid diluent may have a higher boiling point than the terpene, such as a high boiling PAO (e.g., Durasyn® PAOs, such as Durasyn® 164, available from Ineos Oligomers, League City, TX), a higher boiling terpene oil (e.g., squalane).
  • PAO high boiling PAO
  • Durasyn® PAOs such as Durasyn® 164, available from Ineos Oligomers, League City, TX
  • a higher boiling terpene oil e.g., squalane
  • the hydrocarbon terpene is carried through the flow reactor in an inert solvent such as toluene or heptane.
  • a liquid diluent may be selected to be easily separated from the product, e.g. , by distillation.
  • the hydrocarbon terpene is carried through the flow reactor in a gaseous diluent,
  • the multiple stage hydrogenation as described herein may be adapted to a variety of different reactor configurations.
  • multiple catalyst beds are used with interstage coolers.
  • a multiple tube reactor is used.
  • a continuous slurry reactor is used.
  • a fluidized bed reactor is used.
  • multiple hydrogenation stages are configured as multiple zones in a fixed bed reactor.
  • a multi-stage hydrogenation process adapted to a flow through reactor is illustrated in FIGURE 6 and provided in Example 32. If multiple reactors are used in a multistage hydrogenation, any combination of batch reactors and fixed bed or flow through type reactors may be used.
  • the multi-stage hydrogenation is carried out in a batch reactor (e.g., batch slurry reactor), or in a series of more than one batch reactors, wherein one or more stages (e.g. a first stage) is carried out in a first batch reactor and one or more subsequent stages (e.g. a second stage) is carried out in a second batch reactor, and so on.
  • a batch reactor e.g., batch slurry reactor
  • at least one stage (e.g. a first stage or a final stage) of a multi-stage hydrogenation is carried out in a fixed bed or flow through type reactor.
  • more than one stage (e.g., all stages) of a multi-stage hydrogenation is carried out in a fixed bed or flow through type reactor.
  • a first stage of a multi-stage hydrogenation is carried out in a fixed bed or flow through type reactor and a second or subsequent stage is carried out in a batch reactor. In some variations, a first stage of a multi-stage hydrogenation is carried out in a batch reactor and a second or subsequent stage is carried out in a fixed bed or flow through type reactor.
  • the same catalyst is used in a first and subsequent stages, but the reaction time, temnerature and/or hydrogen pressure is varied in the second or subsequent stages.
  • the temperature of the first stage is lower than the temperature of the second or subsequent stage, e.g. the temperature of the first stage is at least about 50°C, 75°C, 100°C, or 150°C lower than the temperature of a second or subsequent stage.
  • the partial hydrogenation is conducted in three or more stages, and the temperature is increased with each stage, e.g., by at least about 50°C. In some variations, the temperature is increased with each stage, but the hydrogen pressure is maintained to be about the same in second and subsequent stages.
  • the hydrogen pressure of the first stage is higher than the pressure of the second or subsequent stage, e.g., the hydrogen pressure of the first stage is about 10-500 psig, or about 20-500 psig higher than the hydrogen pressure of the second or subsequent stage.
  • the temperature is increased with each stage and the hydrogen pressure is decreased with each stage.
  • the loading of the catalyst is varied between a first stage and a subsequent stage.
  • the same catalyst is used in first and second stages, and hydrogen pressure in the first stage is in a range from about 50 psig to about 500 psig (e.g., about 50, 100, 200, 300, 400, or 500 psig) and the temperature in the first stage is in a range from about 40°C to about 160°C (e.g., about 40°C, 50°C, 60°C, 70°C, 80°C, 90°C, 100°C, 1 10°C, 120°C, 130°C, 140°C, 150°C, or 160°C), and the hydrogen pressure in the second stage is in a range from about 10 psig to about 50 psig (e.g., about 10, 20, 30, 40, or 50 psig) and the temperature in the second stage is in a range from about 180°C to about 260°C (e.g., about 180°C, 200°C, 220°C, 240°C, or 260°C).
  • hydrogen pressure in the first stage is in a range from about 50
  • the same catalyst is used in the first and second stages, and the same hydrogen pressure is used in the first and second stages, but the temperature is increased in the second stage relative to the first stage, e.g., the temperature in the second stage may be about 50°C-150°C higher than the first stage.
  • the catalyst and hydrogen pressure are kept constant between the first and second stages, the temperature in the first stage is about 40°C-80°C (e.g., about 40°C, 50°C, 60°C, 70°C, or 80°C) and the temperature in the second stage is in a range from about 100°C to about 200°C (e.g., about 100°C, 120°C, 140°C, 160°C, 180°C, or 200°C).
  • the catalysis conditions (structure of catalyst, type of catalyst, catalyst loading, reaction time, temperature and/or hydrogen pressure) are selected so that the total degree of hydrogenation after a first stage is about 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, or 70%.
  • the catalysis conditions are selected so that the total degree of hydrogenation after a final stage (e.g. after a second stage in a two-stage hydrogenation) is about 50%, 55%, 60%, 65%, 70%, 75% or 80%.
  • the catalysis conditions are selected so that the total degree of hydrogenation after a first stage is about 20-70% (e.g., about 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65% or 70%), and the total degree of hydrogenation after a final stage is about 50-80% (e.g., about 50, 55%, 60%, 65%, 70%, 75% or 80%).
  • the catalysis conditions (structure of catalyst, composition of catalyst, catalyst loading, reaction time, temperature and/or hydrogen pressure) of a first hydrogenation stage are selected to hydrogenate the sample so that at least one olefinic bond in the conjugated diene is selectively hydrogenated.
  • catalysis conditions in a first stage may be selected so that there is less than about 10% starting material (e.g., about 9%, 8%, 7%, 6%, 5%, 4%, 3%, 2%, 1%, 0.5%, 0.3%, less than 0.3%, or no detectable amount as measured by GC-MS).
  • the conjugated diene species is effectively eliminated (e.g.
  • the temperature of a second or subsequent stage may be increased to be 160°C or higher, e.g., about 160°C, 170°C, 180°C, 190°C, 200°C, 210°C, 220°C, 230°C, 240°C, 250°C, or 260°C, without forming significant amounts of thermal dimers.
  • a first stage of the hydrogenation produces less than about 10% of the completely hydrogenated alkane (e.g., about 9%, 8%, 7%, 6%, 5%, 4%, 3%, 2%, 1%, 0.5%, 0.3%, less than 0.3%, or no detectable amount as measured by GC/MS).
  • the catalysis conditions are selected such that there is less than about 10% starting material (e.g.
  • the catalysis conditions (catalyst composition, catalyst structure, reaction time, temperature and/or hydrogen pressure) of a first stage may be selected to produce a mixture comprising predominantly mono-olefins and di-olefins, without producing undesirably high amounts (e.g., greater than about 1%, 3%, 5% or 10%, depending on the application) of completely hydrogenated alkenes or leaving undesirably high amounts (e.g., greater than about 1%, 3%, 5%, or 10%, depending on the application) of starting material.
  • the catalysis conditions of a second stage may be selected to preferentially act on the di-olefins over the mono-olefins, thereby enriching the mono-olefin content without creating a concomitant increase in the amount of saturated alkane.
  • the temperature of a second stage may be increased so that the thermodynamics favor hydrogenation of the di-olefin to make a mono-olefin over hydrogenation of the mono-olefin to make saturated alkane.
  • the catalysis conditions (catalyst composition, catalyst structure, reaction time, temperature and/or hydrogen pressure) of a first stage may be selected to produce a mixture comprising predominantly hexahydrofarnesene and tetrahydrofamesene while producing less than about 10% (e.g., less than 10%, less than 5%, less than 3%, less than 1%, less than 0.5%, or an undetectable amount by GC/MS) farnesene and less than about 10% (e.g., less than 10%, less than 5%, less than 3%, less than 1%, less than 0.5%, or an undetectable amount by GC/MS) farnesane.
  • a catalyst e.g., a palladium catalyst such as ⁇ 7 ⁇ 1 2 ⁇ 3 (e.g., 0.3wt%) or a Pd/C catalyst (e.g., 5wt% or 10wt%) may be used at a temperature in a range of about 80°C-160°C and a hydrogen pressure in a range of about 45 psig- 1000 psig in a first stage to create an intermediate partially hydrogenated farnesene composition comprising predominantly hexahydrofamesene and
  • a second stage using the same catalyst but higher temperature e.g., about 200°C or greater, such as about 200°C, 210°C, 220°C, 240°C or 260°C
  • a hydrogen pressure lower than the first stage e.g., a hydrogen pressure of about 10 psig, 20 psig, 30 psig, 40 psig, 50 psig, 60 psig, 70 psig, 80 psig, 90 psig, or 100 psig
  • a hydrogen pressure e.g., a hydrogen pressure of about 10 psig, 20 psig, 30 psig, 40 psig, 50 psig, 60 psig, 70 psig, 80 psig, 90 psig, or 100 psig
  • the catalysis conditions (catalyst composition, catalyst structure, reaction time, temperature and/or hydrogen pressure) of a first stage may be selected to produce a mixture comprising predominantly hexahydrofamesene and tetrahydrofamesene while producing less than about 10% (e.g., less than 10%, less than 5%, less than 3%, less than 1%, less than 0.5%, or an undetectable amount by GC/MS) farnesene and less than about 10% (e.g., less than 10%, less than 5%, less than 3%, less than 1%, less than 0.5%, or an undetectable amount by GC/MS) farnesane.
  • a catalyst e.g., a palladium catalyst such as ⁇ 7 ⁇ 1 2 ⁇ 3 (e.g., 0.3wt%) or a Pd/C catalyst (e.g., 5wt% or 10wt%) may be used at a temperature in a range of about 80°C-160°C and a hydrogen pressure in a range from about 45 psig- 1000 psig in a first stage to create an intermediate partially hydrogenated farnesene composition comprising predominantly hexahydrofamesene and tetrahydrofamesene, with less than about 5% (e.g., less than about 1% farnesene and less than about 5%) (e.g., less than about 1%) farnesane.
  • a palladium catalyst such as ⁇ 7 ⁇ 1 2 ⁇ 3 (e.g., 0.3wt%) or a Pd/C catalyst (e.g., 5wt% or 10wt%)
  • a second stage using the same catalyst but higher temperature e.g., about 200°C or greater, such as about 200°C, 210°C, 220°C, 240°C or 260°C
  • a hydrogen pressure lower than the first stage e.g., a hydrogen pressure of about 10 psig, 20 psig, 30 psig, 40 psig, 50 psig, 60 psig, 70 psig, 80 psig, 90 psig, or 100 psig
  • a hydrogen pressure lower than the first stage e.g., a hydrogen pressure of about 10 psig, 20 psig, 30 psig, 40 psig, 50 psig, 60 psig, 70 psig, 80 psig, 90 psig, or 100 psig
  • a hydrogen pressure lower than the first stage e.g., a hydrogen pressure of about 10 psig, 20 psig, 30 psig, 40 psig, 50 psig, 60 psig, 70 psig, 80
  • controlled staged partial hydrogenation of ⁇ -farnesene to produce olefinic feedstocks is carried out as follows.
  • One aliquot hydrogen corresponding to one molar equivalent hydrogen per mol ⁇ -farnesene or (two aliquots, each corresponding to about 0.5 mol equivalent H 2 per mol ⁇ -farnesene) may be delivered to a reactor containing ⁇ -farnesene, and the reaction allowed to proceed until the hydrogen is substantially consumed to form 25% hydrogenated ⁇ -farnesene.
  • a first pair of 0.5 mol equivalents of H 2 may be delivered to the reactor and allowed to proceed until the hydrogen is substantially consumed, and a second pair of 0.5 mol equivalents of H 2 may be delivered to the reactor and allowed to proceed until the hydrogen is substantially consumed.
  • a first pair of 0.5 mol equivalents of H 2 is delivered to the reactor and allowed to proceed until the hydrogen is substantially consumed
  • a second pair of 0.5 mol equivalents of H 2 is delivered to the reactor and allowed to proceed until the hydrogen is substantially consumed in a first stage.
  • the reactor is heated (e.g. to about 100°C- 140°C) as the heat generated by the exothermic hydrogenation decreases, and a third pair of 0.5 mol equivalents of H 2 is delivered to the reactor while the reactor is heated to a temperature of about 100°C- 140°C and allowed to proceed until the hydrogen is substantially consumed.
  • the methods comprise reacting a controlled amount of hydrogen with a hydrocarbon terpene having a conjugated diene in the presence of a catalyst under controlled (without involving multiples stages) reaction conditions to produce an olefin comprising partially hydrogenated hydrocarbon terpene, wherein the catalyst and reaction conditions are selected to preferentially hydrogenate at least one olefinic bond in the conjugated diene and to preferentially produce mono-olefin species in the olefin comprising the partially hydrogenated hydrocarbon terpene.
  • ⁇ -farnesene that has been partially hydrogenated to produce partially hydrogenated ⁇ - farnesene in which hexahydrofarnesene has been preferentially produced with less than 0.3% ⁇ -farnesene in a single stage hydrogenation are shown in Examples herein.
  • a single stage partial hydrogenation process can be used to make an olefinic feedstock rich in a desired species (e.g., mono-olefins) if the catalyst is sufficiently selective, whereas a multi-stage partial hydrogenation process is used in those instances in which the catalyst itself is not particularly selective, but the process conditions (e.g., temperature and/or hydrogen pressure) can be changed between a first stage and a second stage to tune the composition of the final olefinic mixture by choosing process conditions that kinetically and/or thermodynamically favor hydrogenation of certain species over others (e.g. , process conditions that favor hydrogenation of polyenes over monoenes to form a mono-olefinic feedstock that comprises limited amounts of alkane).
  • a desired species e.g., mono-olefins
  • the single stage hydrogenation methods comprise reacting a controlled amount of hydrogen with a hydrocarbon terpene having a conjugated diene in the presence of a catalyst under controlled reaction conditions to produce an olefin comprising partially hydrogenated hydrocarbon terpene, wherein the catalyst and reaction conditions are selected to preferentially hydrogenate one olefinic bond in the conjugated diene and to preferentially produce dihydro hydrocarbon terpene species (with one carbon-carbon double bond reduced).
  • the catalyst and reaction conditions are selected to preferentially hydrogenate one olefinic bond in the conjugated diene and to preferentially produce dihydro hydrocarbon terpene species (with one carbon-carbon double bond reduced).
  • Non-limiting examples are shown in Examples 8-9 herein.
  • the resulting dihydro hydrocarbon terpene species may be used as-is as an olefinic feedstock, or may be further hydrogenated in a second stage (in which one or more of or any combination of catalyst, catalyst loading, temperature and hydrogen pressure may be varied relative to the first stage) to produce an olefinic feedstock.
  • the methods comprise reacting a controlled amount of hydrogen with a hydrocarbon terpene having a conjugated diene in the presence of a catalyst under controlled reaction conditions to produce an olefin comprising partially hydrogenated hydrocarbon terpene, wherein the catalyst and reaction conditions are selected to preferentially hydrogenate one olefinic bond in the conjugated diene and to produce predominantly dihydro hydrocarbon terpene species and tetrahydro hydrocarbon terpene species (e.g.
  • the dihydro and tetrahydro species combined make up at least about 75%, at least about 80%, at least about 85%, at least about 90%, or at least about 95% of the partially hydrogenated product), with less than about 5% (or less than about 1%) conjugated hydrocarbon terpene remaining, and less than about 5% (or less than about 1%) alkane formed.
  • the ratio of dihydro:tetrahydro species in the partially hydrogenated mixture is about 50:50, or 40:60, or 60:40. Non- limiting examples are shown in Examples 1 and 12 herein.
  • the resulting mixture may be used as-is as an olefinic feedstock, or may be further hydrogenated in a second stage (in which one or more of or any combination of catalyst, catalyst loading, temperature and hydrogen pressure may be varied relative to the first stage) to produce an olefinic feedstock.
  • the amount of hydrogen, catalyst and catalyst conditions may be selected in a second hydrogenation stage to selectively hydrogenate the tetrahydro species over the dihydro species to result in a composition rich in dihydro species while minimizing formation of alkane.
  • a method for making an olefinic feedstock comprises reacting a controlled amount of hydrogen with a Cio-C 30 hydrocarbon terpene (e.g. ⁇ -farnesene or a-farnesene) in the presence of a catalyst under controlled reaction conditions in a single stage to produce a partially hydrogenated terpene that is rich in mono-olefin and comprises a limited amount of alkane.
  • a catalyst under controlled reaction conditions in a single stage to produce a partially hydrogenated terpene that is rich in mono-olefin and comprises a limited amount of alkane.
  • such methods are capable of producing a composition comprising at least about 60% mono-olefin and less than about 25% alkane.
  • the controlled amount of hydrogen, the catalyst, and the reaction conditions are selected to produce an olefin comprising at least about 65% mono-olefin and less than about 20% alkane. In certain variations, the controlled amount of hydrogen, the catalyst, and the reaction conditions are selected to produce an olefin comprising at least about 70% mono-olefin and less than about 20% alkane. In certain variations, the controlled amount of hydrogen, the catalyst, and the reaction conditions are selected to produce an olefin comprising at least about 75% mono-olefin and less than about 15% alkane, or less than about 10% alkane. In some variations, the hydrocarbon terpene is made by a bioengineered microorganism using a renewable carbon source.
  • a method for making an olefinic feedstock comprises reacting a controlled amount of hydrogen with a Cio-C 30 hydrocarbon terpene (e.g. ⁇ -farnesene or a-farnesene) in the presence of a catalyst under controlled reaction conditions in a single stage to produce a partially hydrogenated terpene comprising a substantial amount of mono-olefin and a limited amount of di-olefin.
  • a method for making an olefinic feedstock comprises reacting a controlled amount of hydrogen with a Cio-C 30 hydrocarbon terpene (e.g. ⁇ -farnesene or a-farnesene) in the presence of a catalyst under controlled reaction conditions in a single stage to produce a partially hydrogenated terpene comprising a substantial amount of mono-olefin and a limited amount of di-olefin.
  • any di-olefin that is present may be substantially unconjugated, e.g., so that an amount of
  • Such methods may be selected when a feedstock rich in mono-olefins is desired and di-olefins cause undesired side reactions, cross-products, and the like.
  • the methods are capable of producing a mono-olefinic feedstock comprising at least about 50% mono-olefin and about 10% or less di-olefin, at least about 50% mono-olefin and about 5% or less di-olefin, at least about 50% mono-olefin and about 3% or less di-olefin, at least about 55% mono-olefin and about 10% or less di-olefin, at least about 55% mono-olefin and about 5% or less di-olefin, at least about 55% mono-olefin and about 3% or less di-olefin, at least about 60% mono-olefin and about 10% or less di-olefin, at least about 60% mono-olefin and about 5% or less di- olefin, at least
  • a method for making an olefinic feedstock comprises reacting a controlled amount of hydrogen with a Cio-C 30 hydrocarbon terpene (e.g. ⁇ -farnesene or a-farnesene) in the presence of a catalyst under controlled reaction conditions in a multiple stages (e.g., two or more stages) to produce a partially hydrogenated terpene rich in mono-olefin and comprising a limited amount of alkane.
  • a method for producing a partially hydrogenated terpene comprising at least about 60% mono-olefin and less than about 25% alkane.
  • the controlled amount of hydrogen, the catalyst, and the reaction conditions are selected to produce an olefin comprising at least about 65% mono-olefin and less than about 20% alkane. In certain variations, the controlled amount of hydrogen, the catalyst, and the reaction conditions are selected to produce an olefin comprising at least about 70% mono-olefin and less than about 20% alkane. In certain variations, the controlled amount of hydrogen, the catalyst, and the reaction conditions are selected to produce an olefin comprising at least about 75% mono-olefin and less than about 15% alkane, or less than about 10% alkane. In some variations, the hydrocarbon terpene is made by a bioengineered microorganism using a renewable carbon source.
  • At least one of the group consisting of catalyst, catalyst loading, temperature, and hydrogen pressure is varied between a first stage and a subsequent stage of the multi-stage reaction.
  • the hydrocarbon terpene is made by a bioengineered microorganism using a renewable carbon source.
  • a method for making an olefinic feedstock comprises reacting a controlled amount of hydrogen with a Cio-C 30 hydrocarbon terpene (e.g. ⁇ -farnesene or a-farnesene) in the presence of a catalyst under controlled reaction conditions in a multiple stages (e.g., two or more stages) to produce a partially hydrogenated terpene rich in mono-olefin and comprising a limited amount of di-olefin.
  • a method for producing an olefinic feedstock comprises reacting a controlled amount of hydrogen with a Cio-C 30 hydrocarbon terpene (e.g. ⁇ -farnesene or a-farnesene) in the presence of a catalyst under controlled reaction conditions in a multiple stages (e.g., two or more stages) to produce a partially hydrogenated terpene rich in mono-olefin and comprising a limited amount of di-olefin.
  • such methods are capable of producing a partially hydrogenated terpen
  • any di-olefin that is present may be substantially unconjugated, e.g., so that an amount of conjugated species in the composition is about 2% or less or about 1% or less.
  • Such methods may be selected when a feedstock rich in mono-olefins is desired and di-olefins cause undesired side reactions, cross-products, and the like.
  • the methods are capable of producing a mono-olefinic feedstock comprising at least about 50% mono-olefin and about 10% or less di-olefin, at least about 50% mono-olefin and about 5% or less di- olefin, at least about 50% mono-olefin and about 3% or less di-olefin, at least about 55% mono-olefin and about 10% or less di-olefin, at least about 55% mono-olefin and about 5% or less di-olefin, at least about 55% mono-olefin and about 3% or less di-olefin, at least about 60% mono-olefin and about 10% or less di- olefin, at least about 60% mono-olefin and about 5% or less di-olefin, at least about 60% mono-olefin and about 5% or less di-olefin, at least about 60% mono-olefin and about 3% or less di-olefin, at least about
  • any suitable hydrogenation catalyst may be used.
  • a catalyst used for first and/or subsequent hydrogenation stages is selected from the group consisting of Pd, Pt, Ni, Ru, Ir, Cu, Fe, Raney-type porous catalysts such as Ni/Al, Co/Al and Cu/Al, alloys of platinum group catalysts with promoters or stabilizers such as Mo, Co, Mg and Zn, and hydroprocessing catalysts such as NiMoS and CoMoS.
  • Exemplary catalysts are described in U.S. Pat. Nos. 6,403,844; 5,378,767; 5, 151, 172; and 3,702,348, each of which is incorporated herein by reference in its entirety.
  • the catalyst used for first and/or subsequent hydrogenation stages is or comprises Pd/C, e.g. 5wt% Pd/C or 10wt% Pd/C.
  • the catalyst for first and/or subsequent hydrogenation stages is or comprises Pd/Al 2 0 3 , e.g. 0.3wt% Pd/Al 2 0 3 .
  • the catalyst for first and/or subsequent hydrogenation stages is or comprises a Lindlar catalyst, e.g., Pd on calcium carbonate or barium carbonate and treated with lead (e.g., lead oxide or lead acetate).
  • a Lindlar catalyst comprising Pd/Pb/BaC0 3 may be used.
  • the catalyst for first and/or subsequent hydrogenation stages is or comprises Ni, e.g. Raney Ni, sponge nickel, or skeletal nickel.
  • a nickel catalyst is used that is supported by AI 2 O 3 , e.g. about 20%, 12% or 8% N1/AI 2 O 3 .
  • the catalyst used for first and/or subsequent hydrogenation stages comprises nickel sulfide.
  • the catalyst used for first and/or subsequent hydrogenation stages comprises molybdenum sulfide, e.g. molybdenum sulfide catalysts having a Mo:S ratio of sulfur to molybdenum, e.g. MoS 2 supported on alumina, e.g.
  • activated alumina having a surface area of about 300 square meters per gram or more, or silica gel, activated charcoal, acid treated clay, silica-alumina complexes, e.g. as disclosed in U.S. Pat. No. 2,674,634 which is incorporated by reference herein in its entirety.
  • the catalyst can be provided in any suitable form, e.g. with a minimum dimension of at least about 1mm. Particle dimensions may be selected depending on catalyst type and catalysis conditions (e.g. slurry batch, fixed bed, fluidized bed, or continuous flow reactor).
  • the catalyst may be selected to have a specified surface area to produce the desired distribution of partially hydrogenated hydrocarbon terpene species, and may be formed in any suitable form factor, e.g. cylinders, tablets, granules, spheres, lobed cylinders, and the like.
  • the catalyst contains voids, e.g. in the form of channels, passages, or holes.
  • the catalyst used for first and/or subsequent hydrogenation stages comprises a shell type catalyst.
  • the catalyst comprises an extrudate, e.g., an extrude having a desired cross-sectional shape, such as a lobed extrude (e.g., trilobe extrudate).
  • the catalyst used for first and/or subsequent stages is or comprises Pu7Al 2 0 3 , e.g., 0.3wt% Pd/Al 2 0 3 tribobe extrudate.
  • a continuous flow reactor scheme may be designed to incorporate the multistage
  • any of the hydrogenation processes described herein may be adapted to a continuous flow reactor using known techniques for supporting catalysts, selecting appropriate diluents, providing heat and temperature control, providing hydrogen and pressure control, and separation of product from diluents, byproducts, residual starting material and impurities.
  • two reactors are placed in series, where the temperature in the first reactor is in a range from about 80°C to about 1 10°C and the hydrogen pressure in the first reactor is in a range from about 50-300 psig, and the temperature in the second reactor is in a range from about 160°C to about 240°C and the hydrogen pressure in the second reactor is in a range from about 10-40 psig.
  • three reactors are placed in series, where the first reactor is self-heated and the hydrogen pressure in the first reactor is in a range from about 50-300 psig, the temperature in the second reactor is in a range from about 80°C to about 240°C and the hydrogen pressure in the second reactor is in a range from about 50-300 psig, and the temperature in the third reactor is in a range from about 160°C to about 240°C and the hydrogen pressure in the third reactor is in a range from about 10-40 psig.
  • catalysts used in each of the reactors may be the same or different.
  • a catalyst comprising Pd (e.g., PCI/AI 2 O 3 ) is used in some or all series reactors in a continuous flow reactor scheme. In other variations, the catalyst is different in series reactors in a continuous flow reactor scheme.
  • a catalyst that selectively catalyzes hydrogenation of conjugated dienes may be used in a first reactor in some variations.
  • a catalyst that selectively hydrogenates dienes is used in a final reactor.
  • a catalyst that selectively catalyzes dehydrogenation of paraffins to form mono-olefins may be used in a final reactor.
  • a single continuous flow reactor with multiple zones in series is used to carry out staged partial hydrogenation as described herein.
  • the temperature and hydrogen pressure and catalyst may each be independently varied between zones to achieve a staged hydrogenation process as described herein within a single reactor.
  • Any multi-zone reactor known in the art may be adapted for this purpose, and known techniques for use of diluents, catalyst support, heating and temperature control, feeding in of hydrogen and pressure control, and separation of products from diluents, reactants, byproducts, impurities and the like may be used.
  • a reactor comprises two zones in series, where the temperature in the first zone is in a range from about 80°C to about 1 10°C and the hydrogen pressure in the first zone is in a range from about 50-300 psig, and the temperature in the second zone is in a range from about 160°C to about 240°C and the hydrogen pressure in the second zone is in a range from about 10-40 psig.
  • a reactor comprises three zones in series, where the first zone is self-heated and the hydrogen pressure in the first zone is in a range from about 50-300 psig, the temperature in the second zone is in a range from about 80°C to about 240°C and the hydrogen pressure in the second zone is in a range from about 50-300 psig, and the temperature in the third zone is in a range from about 160°C to about 240°C and the hydrogen pressure in the third zone is in a range from about 10- 40 psig.
  • catalysts used in each of the zones may be the same or different.
  • a catalyst comprising Pd e.g., PCI/AI 2 O 3
  • the catalyst is different between zones.
  • a catalyst that selectively catalyzes hydrogenation of conjugated dienes may be used in a first zone, or in first and second zones in some variations.
  • a catalyst that selectively hydrogenates dienes is used in a final zone.
  • a catalyst that selectively catalyzes dehydrogenation of paraffins to form mono-olefins may be used in a final zone.
  • any suitable support can be used, e.g. carbon, silica, titania, zirconia, alumina, kieselguhr, magnesia, calcium aluminate cements, and other inorganic materials.
  • supports are activated.
  • Modified versions of such supports can be used, e.g. base-treated supports or supports treated with stabilizing additives such as MgO.
  • a support can have any suitable form factor (e.g. a pellet or extrudate) with dimensions on the order of about 0.1 -5mm, 0.5-5mm, l-5mm, 1- 4mm, or l-3mm.
  • the hydrogenation catalyst may be used in any effective loading. In some variations (e.g. for
  • an effective catalyst loading may be about 1/50, 1/100, 1/1000, 2/1000, 3/1000, 4/1000, 5/1000, 1/2000, 1/5000, or 1/10000 (ratio refers to weight metal/weight substrate).
  • ⁇ -farnesene can be partially hydrogenated using 5wt% Pd/C at a loading of 1/10000, 1/7000, 1/6000, 1/5000, 1/4000, 1/3000, 1/2000, 1/1000, 2/1000, 3/1000, 4/1000, or 5/1000.
  • an effective catalyst loading may be about 1/50, 1/100, 1/200, 1/300, 1/400, 1/500, 1/750, 1/1000, 1/2000, 1/5000, 1/10000 g metal/g substrate, or in a range from about 10-lOOOppm, 10-lOOppm, (e.g., 10-60ppm), where ppm refers to g metal/g substrate.
  • an effective catalyst loading may be about 10 ppm, about 12 ppm, about 14 ppm, about 16 ppm, about 18 ppm, about 20 ppm, about 30 ppm, about 40 ppm, about 50 ppm, about 60 ppm, about 70 ppm, about 80 ppm, about 90 ppm, or about 100 ppm in a first or a second hydrogenation stage.
  • a controlled amount of hydrogen under controlled reaction conditions so as to control the extent of and site selectivity of the hydrogenation.
  • Such controlled hydrogenation can be accomplished in a variety of ways, and using a variety of equipment setups.
  • continuous hydrogen uptake by the sample may be controlled and/or measured using a flow meter, flow totalizer, or the like, or hydrogen may be delivered to the sample in discrete or quantized molar aliquots, e.g. discrete aliquots of 0.25, 0.5, or 1 mol H 2 per mol hydrocarbon terpene.
  • a batch slurry hydrogenation reactor is used.
  • a fixed bed reactor is used for partial hydrogenation.
  • a fluidized bed reactor is used for partial hydrogenation.
  • the temperature of the hydrogenation may be selected to control the rate of reaction, which may, in some situations, enhance site selectivity of the hydrogenation.
  • a suitable hydrogenation temperature is in a range from about 40°C to about 260°C, e.g. about 40°C, 50°C, 60°C, 70°C, 80°C, 90°C, 100°C, 1 10°C, 120°C, 130°C, 140°C, 150°C, 160°C, 170°C, 180°C, 190°C, 200°C, 210°C, 220°C, 230°C, 240°C, 250°C, or 260°C.
  • the reaction is conducted at about 80°C.
  • the reaction is conducted at about 100°C.
  • the reaction temperature is varied between a first stage and a subsequent stage.
  • the reaction is at least partially self-heated during a first stage when the exothermic reaction is generating sufficient heat, and external heat is added (e.g., to heat the reaction to about 140°C, 150°C or 160°C) during a latter stage.
  • the reactor is cooled to keep the temperature of the exothermic hydrogenation process under control.
  • the hydrogen pressure used may be in a range from about 20 psig- 1000 psig, e.g. about 20, 30, 40, 50, 75, 100, 125, 150, 175, 200, 225, 250, 275, 300, 325, 350, 375, 400, 425, 450, 475, 500, 525, 550, 575, 600, 625, 650, 675, 700, 725, 750, 775, 800, 825, 850, 875, 900, 925, 950, 975, or 1000 psig.
  • the hydrogen pressure is varied between a first stage and a subsequent stage of the hydrogenation.
  • One variation of method for carrying out at least one stage of partially hydrogenating famesene comprises immersing a catalyst into the liquid hydrocarbon terpene (e.g. ⁇ -farnesene) to form a slurry and delivering a controlled amount of hydrogen to the slurry in a closed reactor, where the controlled amount of hydrogen corresponds to a molar equivalent of desired hydrogenation degree.
  • the method comprises hydrogenating the terpene at a temperature between about 50°C and 260°C until the controlled amount of hydrogen is substantially consumed, and removing the catalyst from the
  • one molar equivalent of hydrogen delivered to the slurry in the closed reactor corresponds to 25% hydrogenation
  • two molar equivalents of hydrogen delivered to the slurry in the closed reactor corresponds to 50% hydrogenation
  • three molar equivalents corresponds to 75% hydrogenation.
  • the controlled amount of hydrogen may be delivered to the slurry in one or more discrete aliquots or as a continuous stream.
  • molar equivalents of hydrogen are delivered to the slurry (e.g.
  • a controlled amount of hydrogen is delivered to a closed reactor in a continuous stream.
  • a catalyst e.g. 5wt% Pd/C or 10wt% Pd/C
  • liquid hydrocarbon terpene e.g. ⁇ -farnesene
  • the reactor is evacuated.
  • Hydrogen is delivered to the reactor (e.g. at about 50 psig), and the cumulative uptake of hydrogen is monitored, e.g. using a flow totalizer or a flow meter.
  • the temperature of the reaction is controlled to control the rate of reaction, e.g.
  • Cio olefin comprising partially hydrogenated myrcene, a Cio olefin comprising partially hydrogenated ocimene, a Ci 5 olefin comprising partially hydrogenated ⁇ -farnesene, a Ci 5 olefin comprising partially hydrogenated a-farnesene, a C20 olefin comprising partially hydrogenated springene, a C25 olefin comprising partially hydrogenated geranylfamesene, a C30 olefin comprising partially hydrogenated isodehydrosqualene, or a C30 olefin comprising partially hydrogenated isosqualane precursor I or II.
  • microbial-derived farnesene is partially hydrogenated to produce a feedstock comprising a mixture of Ci 5 trienes.
  • delivering a controlled amount of hydrogen (1 mol equivalent hydrogen) under controlled reaction conditions with a suitable catalyst (5 wt% Pd/C at a loading of 3g/kg) yields an olefinic mixture comprising almost exclusively dihydrofarnesene, with less than 10% of the mono-olefin molecules exhibiting a conjugated diene moeity.
  • Example 9 delivering a controlled amount of hydrogen (1 molar equivalent of hydrogen) under controlled reaction conditions with a Lindlar catalyst yields an olefinic mixture comprising almost exclusively dihydrofarnesene, with less than 12% of the mixture attributed to tetrahydrofarnesene.
  • the methods described herein may be used to produce a partially hydrogenated ⁇ -farnesene feedstock that comprises about 60, 65, 70, 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89 or 90% hexahydrofarnesene.
  • partially hydrogenated farnesene produced by delivering about 2.4-3.4 (or about 2.5-3.2, or about 2.7-3.1) mol equivalents H 2 /mol farnesene in a controlled manner or multistage as described herein may comprise about 50, 55, 60, 65, 70, 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89 or 90% hexahydrofarnesene.
  • the amount of hydrogen delivered can be carefully controlled to achieve a desired balance between mono-olefinic, di-olefinic and alkane species.
  • the olefinic feedstocks derived from partially hydrogenated hydrocarbon terpenes using the methods disclosed herein are suitable for catalytic oligomerization to form a mixture of isoparaffins.
  • at least a portion of the mixture of isoparaffins so produced may be used as a base oil.
  • the olefinic feedstocks derived from partially hydrogenated hydrocarbon terpenes using the methods disclosed herein are suitable for catalytic reaction with one or more alphaolefins to form a mixture of isoparaffins comprising adducts of the terpene and the one or more alphaolefins.
  • at least a portion of the mixture of isoparaffins so produced may be used as a base oil.
  • base oils that are produced using olefinic feedstocks described herein are described in U.S. provisional patent application 61/475,221 filed 13-Apr-2011, U.S.
  • Methods are disclosed herein that comprise using an olefinic feedstock comprising a partially hydrogenated C 10 -C30 hydrocarbon terpene as a monomer or reactant in any industrial process, e.g., an industrial oligomerization, polymerization, hydroformylation, or carbonylation process.
  • Products produced by such methods are disclosed, e.g. alcohols, detergents, surfactants, polymers, plastics, rubbers, or oils.
  • a conjugated alkene e.g. a Cio-C 30 hydrocarbon terpene such as myrcene, ocimene or farnesene
  • a mixture comprising molecules having different degrees of hydrogenation may be produced.
  • conjugated alkenes containing a conjugated diene and at least one additional olefmic bond partial hydrogenation (e.g. with about 2 molar equivalents of hydrogen, or about 1 molar equivalent or less of hydrogen) may preferentially reduce or eliminate at least one olefmic bond of the conjugated diene moiety, as described herein.
  • Partial hydrogenation of a conjugated alkene may result in a distribution of species.
  • myrcene can be partially hydrogenated to result in distribution of hexahydromyrcene, tetrahydromyrcene, dihydromyrcene, and myrcene.
  • Farnesene can be partially hydrogenated to result in a distribution of farnesane, hexahydrofarnesene, tetrahydrofarnesene, dihydrofarnesene, and farnesene.
  • the distribution of species produced by partial hydrogenation can be tuned through selecting the type, activity and loading of the catalyst, and the catalysis conditions (e.g. temperature and/or controlled hydrogen delivery).
  • the hydrogenation may be accomplished in two or more stages to produce a desired distribution of species in a partially hydrogenated terpene hydrocarbon.
  • the amount of hydrogen, catalysis conditions (structure and type of catalyst, catalyst loading, reaction time, temperature and/or hydrogen pressure) of a first stage may be selected to produce an intermediate distribution of species
  • the amount of hydrogen and catalysis conditions (structure and type of catalyst, temperature and/or hydrogen pressure) for a second hydrogenation stage may be selected based on the intermediate distribution of species formed in the first stage to produce a desired final distribution of species.
  • the catalysis conditions of a second stage may be selected so as to minimize formation of alkane.
  • the catalysis conditions may be selected so that partial hydrogenation of a hydrocarbon terpene (e.g. myrcene, ocimene, or farnesene) results in a distribution that is unexpectedly rich in mono-olefinic species.
  • a hydrocarbon terpene e.g. myrcene, ocimene, or farnesene
  • Myrcene can be hydrogenated to produce partially hydrogenated myrcene in which tetrahydromyrcene is the predominant species (e.g. at least about 50%, 55%, 60%, 70% or 80% of the sample is
  • Farnesene can be hydrogenated to produce partially hydrogenated farnesene in which hexahydrofarnesene is the predominant species (e.g. at least about 50%, 55%, 60%, 70% or 80% of the sample is hexahydrofarnesene).
  • the hydrogenation is conducted in a single stage, and the catalyst and/or catalysis conditions are selected to provide a desired distribution of species.
  • a catalyst and catalyst conditions that are known to selectively reduce at least one olefinic bond in a conjugated diene moiety may be used to produce a composition rich in tri-olefinic species.
  • a catalyst and catalysis conditions that are known to selectively produce mono-olefins may be used to produce a composition rich in mono-olefinic species.
  • compositions for olefinic feedstocks derived by partial hydrogenation of conjugated hydrocarbon terpenes are disclosed herein: i) olefinic feedstocks compositions that have very low amounts of conjugated dienes (e.g., less than about 10% conjugated diene, less than about 5% conjugated diene, or less than about 1% conjugated diene); ii) olefinic feedstocks comprised predominantly of mono- olefins and di-olefins (e.g., at least about 80%, or at least about 90%, or at least about 95% mono-olefins and di-olefins); iii) olefinic feedstock compositions comprised predominantly of mono-olefinic species (e.g., at least about 60%, at least about 65%, at least about 70%, at least about 75%, or at least about 80% mono
  • di-olefins that are present may be substantially unconjugated, e.g., so that a composition comprises at most about 2%, at most about 1%, at most about 0.5%, at most about 0.1%, or no detectable conjugated species.
  • Partially hydrogenated a-farnesene or ⁇ -farnesene may comprise any amount of and any combination of dihydrofarnesene, tetrahydrofarnesene, hexahydrofarnesene, farnesane, and farnesene.
  • dihydrofarnesene tetrahydrofarnesene
  • hexahydrofarnesene farnesane
  • farnesene e.g., exemplary structures for various species of dihydrofarnesene, tetrahydrofarnesene and hexahydrofarnesene are shown below.
  • Partially hydrogenated myrcene may comprise any amount of, and any combination of, dihydromyrcene, tetrahydromyrcene, 2,6-dimethyloctane, and myrcene.
  • dihydromyrcene tetrahydromyrcene
  • 2,6-dimethyloctane a compound that has a high degree of hydrophilicity
  • myrcene Nonlimiting exemplary structures for various species of dihydromyrcene and tetrahydromyrcene are shown below.
  • Partially hydrogenated ocimene may comprise any amount of and any combination of dihydroocimene, tetrahydroocimene, 2,6-dimethyloctane, and ocimene.
  • dihydroocimene tetrahydroocimene
  • 2,6-dimethyloctane 2,6-dimethyloctane
  • ocimene ocimene
  • Tetrahydroocimene ng any isomers of the foregoing.
  • the degree of hydrogenation in a partially hydrogenated hydrocarbon terpene (e.g., farnesene) sample can be quantified by a variety of methods, e.g. by mol of H 2 consumed per mol hydrocarbon terpene (e.g. per mol farnesene) in the hydrogenation process, by an analysis of the degree of unsaturation in the sample (e.g.
  • Bromine number which may be measured according to ASTM Dl 159-07 "Standard Test Method for Bromine Numbers of Petroleum Distillates and Commercial Aliphatic Olefins by Electrometric Titration” which is incorporated herein by reference in its entirety, or by Bromine index, which may be measured according to ASTM D2710-09 "Standard Test Method for Bromine Index of Petroleum Hydrocarbons by Electrometric Titration” which is incorporated herein by reference in its entirety), or by measuring the relative populations of each species (e.g., farnesene, farnesane,
  • hexahydrofarnesene, tetrahydrofamesene, and dihydrofamesene e.g. by GC-MS or GC-FID.
  • species in a partially hydrogenated sample may be determined by GC-MS or GC-FID as follows. Peak areas associated with ions corresponding to each of farnesane, hexahydrofarnesene, tetrahydrofamesene, and dihydrofamesene can be calculated, and the resulting relative populations of each species can be determined.
  • the degree of unsaturation e.g.
  • Table 1 shows a theoretical correlation between % unsaturation and Bromine number, assuming that partially hydrogenated farnesene responds to bromine as a tri-unsaturate.
  • An experimentally measured Bromine number may be used to estimate a % hydrogenation in a sample using Table 1.
  • An experimentally measured % hydrogenation (e.g., by GC-FID or GC-MS) can be used to estimate a Br number in a number using Table 1.
  • Table 1 provides an expected Bromine number for various partially hydrogenated farnesene feedstocks.
  • the feedstock may comprise hexahydrofamesene, tetrahydrofamesene and famesane.
  • the feedstock may comprise hexahydrofamesene, tetrahydrofamesene and
  • feedstocks may comprise hexahydrofamesene, tetrahydrofamesene,
  • feedstocks may comprise hexahydrofamesene, tetrahydrofenesene, dihydrofamesene, famesane, and farnesene (or an isomer thereof).
  • partially hydrogenated myrcene used as a feedstock comprises tetrahydromyrcene, and, in certain variations, may additionally comprise dihydromyrcene and/or hexahydromyrcene.
  • Partially hydrogenated ocimene used as a feedstock comprises tetrahydroocimene and may, in certain variations, additionally comprise dihydroocimene and/or hexahydroocimene.
  • feedstocks in which the partial hydrogenation proceeds so as to selectively reduce at least one olefinic bond in a conjugated diene moiety in a hydrocarbon terpene e.g. a C10-C30 hydrocarbon terpene such as myrcene, ocimene, or farnesene (e.g. ⁇ -farnesene)
  • a hydrocarbon terpene e.g. a C10-C30 hydrocarbon terpene such as myrcene, ocimene, or farnesene (e.g. ⁇ -farnesene)
  • some feedstocks comprise partially hydrogenated ⁇ -farnesene in which the partial hydrogenation proceeds so as to selectively reduce the conjugated diene, so that a sample that is 25% hydrogenated consists essentially of dihydrofarnesene (e.g. one or more dihydrofarnesene structures shown in Examples 8 and 9 herein).
  • feedstocks in which the partial hydrogenation proceeds so as to selectively produce a mono-olefin e.g. hexahydrofamesene in the case of farnesene (e.g. ⁇ -farnesene) and tetrahydromyrcene in the case of myrcene
  • a mono-olefin e.g. hexahydrofamesene in the case of farnesene (e.g. ⁇ -farnesene) and tetrahydromyrcene in the case of myrcene
  • the mono-olefin-rich feedstock produced from partial hydrogenation of hydrocarbon terpenes e.g.
  • hydrocarbon terpenes microbially produced via genetically engineered cells using a renewable carbon source as described herein can be used in place of, or in addition to, an olefmic feedstock derived from fossil fuel sources (e.g. a linear or branched mono-olefin or a linear or branched alpha-olefin derived from petroleum products).
  • an olefmic feedstock derived from fossil fuel sources e.g. a linear or branched mono-olefin or a linear or branched alpha-olefin derived from petroleum products.
  • olefmic feedstocks comprising partially
  • hydrocarbon terpene e.g. myrcene, ocimene, or farnesene
  • the partially hydrogenated hydrocarbon terpene comprises at least about 60% mono-olefin and less than about 25% alkane.
  • the hydrocarbon terpene is produced by bioengineered
  • the olefmic feedstock comprises at least about 65% mono-olefin and less than about 25% alkane. In some variations, the olefmic feedstock comprises at least about 70% mono-olefin and less than about 20% alkane. In some variations, the olefmic feedstock of comprises at least about 75% mono-olefin and about 10% or less alkane. For example, some olefmic feedstocks comprise at least about 60% hexahydrofamesene and less than about 25% famesane, at least about 65% hexahydrofamesene and less than about 25% famesane, at least about 70%
  • ⁇ -farnesene used to make the feedstocks is made by bioengineered microorganisms using a renewable carbon source.
  • feedstock compositions derived from ⁇ -farnesene that are about 60-80% (e.g. about 60%, 61%, 62%, 63%, 64%, 65%, 66%, 67%. 68%. 69%, 70%, 71%, 72%, 73%, 74%, 75%, 76%, 77%, 78%, 79%, or 80%) hydrogenated and hexahydrofamesene is produced in an amount greater than about 50%, e.g. hexahydrofamesene is present at about 50-80% of the total partially hydrogenated farnesene sample, e.g. about 50, 55, 60, 65, 70, 75, or 80% (as measured by area%).
  • hexahydrofarnesene-rich feedstock can be used in place of, or in addition to an olefmic feedstock having a similar molecular weight (e.g. a linear or branched mono-olefin, or a linear or branched alpha-olefin).
  • the hexahydrofarnesene-rich feedstock may be used in place of or in addition to a C12-Q5 linear or branched mono-olefin derived from fossil fuels.
  • the hexahydrofarnesene-rich feedstock may be used to substitute for or to supplement a C12-C15 linear or branched alpha-olefin feedstock.
  • feedstock compositions derived from ⁇ -farnesene that are about 70-80% (e.g. about 70%, 71%, 72%, 73%, 74%, 75%, 76%, 77%, 78%, 79%, or 80%) hydrogenated and hexahydrofamesene is produced in an amount greater than about 50%, e.g. hexahydrofamesene is present at about 50-80% of the total partially hydrogenated famesene sample, e.g. about 50, 55, 60, 65, 70, 75 or 80%.
  • the hexahydrofamesene -rich feedstock may be used in place of, or in addition to an olefinic feedstock having a similar molecular weight (e.g. a linear or branched mono-olefin, or a linear or branched alpha-olefin).
  • the hexahydrofarnesene-rich feedstock may be used in place of or in addition to a C12-C15 linear or branched mono-olefin derived from fossil fuels.
  • the hexahydrofarnesene-rich feedstock may be used in place of or in addition to a C12-C15 linear or branched mono-olefin derived from fossil fuels.
  • hexahydrofamesene -rich feedstock may be used to substitute for or to supplement a C12-C15 linear or branched alpha-olefin feedstock.
  • feedstock compositions derived from myrcene that are about 60-70% (e.g. about 60%, 61%, 62%, 63%, 64%, 65%, 66%, 67%, 68%, 69% or 70%) hydrogenated and tetrahydromyrcene is produced in an amount greater than about 50% (e.g. about 50, 55, 60, 65, 70, 75, 80, 85, 90 or 95%).
  • the tetrahydromyrcene -rich feedstock may be used in place of, or in addition to, an olefinic feedstock
  • a feedstock comprises partially hydrogenated ⁇ -farnesene in which least about 2 but less than about 3.8 mol H 2 was consumed per mol ⁇ -farnesene during hydrogenation. In some variations, a feedstock comprises partially hydrogenated ⁇ -farnesene in which about 2, 2.25, 2.5, 2.75, 3, 3.25 or 3.5 mol H 2 was consumed per mol ⁇ -farnesene during hydrogenation. In some variations, a feedstock comprises partially hydrogenated ⁇ -farnesene in which about 2.5, 2.6, 2.7, 2.8, 2.9, 3.0, 3.1, 3.2, 3.3, 3.4 or 3.5 mol H 2 was consumed per mol ⁇ -farnesene during hydrogenation.
  • a feedstock comprises partially hydrogenated ⁇ -farnesene in which the degree of hydrogenation is about 60- 85%, e.g. about 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80, 81, 82, 83, 84 or 85%, corresponding to about 2.5 to about 3.5 mol H 2 (e.g. 2.5, 2.6, 2.7, 2.8, 2.9, 3.0, 3.1, 3.2, 3.3, 3.4 or 3.5 mol H 2 ) per mol ⁇ -farnesene consumed during hydrogenation.
  • the degree of hydrogenation is about 60- 85%, e.g. about 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80, 81
  • a partially hydrogenated ⁇ -farnesene feedstock comprises at least about 50% hexahydrofamesene, e.g. about 50, 55, 60, 65, 70, 75, or 80% hexahydrofamesane.
  • a partially hydrogenated famesene feedstock comprises at least about 50% hexahydrofamesene (e.g. about 50, 55, 60, 65, 70, 75 or 80%) and less than about 10% (e.g. less than about 10%, less than about 5%, less than about 4%, less than about 3%, less than about 2%, or less than about 1%)
  • a partially hydrogenated famesene feedstock comprises at least about 50% hexahydrofamesene (e.g. about 50, 55, 60, 65, 70, 75 or 80%) and about 5% or less (e.g. less than about 5%, less than about 4%, less than about 3%, less than about 2%, or less than about 1%) famesene (or isomers thereof).
  • a partially hydrogenated famesene feedstock comprises at least about 50% hexahydrofamesene (e.g.
  • a partially hydrogenated farnesene feedstock comprises at least about 50% hexahydrofarnesene (e.g. about 50, 55, 60, 65, 70, 75 or 80%) and about 25% or less farnesane, e.g.
  • some partially hydrogenated farnesene feedstocks comprise about 60-80% hexahydrofarnesene, and about 5-25% farnesane.
  • a partially hydrogenated farnesene feedstock comprises at least about 50% hexahydrofarnesene (e.g. about 50, 55, 60, 65, 70, 75 or 80%) and about 25% or less tetrahydrofarnesene, e.g. about 25% or less, 24% or less, 23% or less, 22% or less, 21% or less, 20% or less, 19% or less, 18% or less, 17% or less, 16% or less, 15% or less, 14% or less, 13% or less, 12% or less, 1 1% or less, or 10% or less tetrahydrofarnesene.
  • hexahydrofarnesene e.g. about 50, 55, 60, 65, 70, 75 or 80%
  • tetrahydrofarnesene e.g. about 25% or less, 24% or less, 23% or less, 22% or less, 21% or less, 20% or less, 19% or less, 18% or less, 17% or less, 16% or less
  • a partially hydrogenated farnesene feedstock comprises at least about 50%, or at least about 60% hexahydrofarnesene (e.g. about 50, 55, 60, 65, 70, 75 or 80%), about 25% or less farnesane, (e.g.
  • feedstocks comprise about 25% or less, 24% or less, 23% or less, 22% or less, 21% or less, 20% or less, 19% or less, 18% or less, 17% or less, 16% or less, 15% or less, 14% or less, 13% or less, 12% or less, 1 1% or less, or 10%).
  • some feedstocks comprise about 50-80%
  • feedstocks comprise about 60-80% hexahydrofarnesene, about 0-15% tetrahydrofarnesene, and about 5-25% farnesane.
  • feedstocks comprise about 65-80% hexahydrofarnesene, about 0-5%
  • compositions of partially hydrogenated farnesene feedstocks are provided in Table 2A.
  • Each "X” specifically discloses a feedstock comprising
  • the amount of aromatic compounds may be less than about lppm.
  • the amount of sulfur and the amount of aromatic compounds may each be less than lppm.
  • the terpene is microbially derived from renewable carbon sources, and has a renewable carbon content of about 100%.
  • each of the compositions specifically disclosed in Table 2A individually, and about 25% or less tetrahydrofamesene, e.g. about 25, 24, 23, 22, 21, 20, 19, 18, 17, 16, 15, 14, 13, 12, 1 1, 10, 9, 8, 7, 6, 5, 4, 3, 2, or %, or no detectable amount of tetrahydrofamesene, individually.
  • each of the compositions specifically disclosed in Table 2A individually, and about 10% or less tetrahydrofamesene, e.g. about 10, 9, 8, 7, 6, 5, 4, 3, 2, or %, or no detectable amount of tetrahydrofamesene, individually.
  • compositions specifically disclosed in Table 2A individually, and about 6% or less tetrahydrofamesene, e.g. about 5, 4, 3, 2, or %, or no detectable amount of tetrahydrofamesene, individually.
  • some feedstocks comprise about at least about 70-80% hexahydrofamesene, about 5-10% famesane, and about 10-20% tetrahydrofamesene.
  • Some feedstocks comprise at least about 70-80% hexahydrofamesene, about 5-15% famesane, and about 5% or less tetrahydrofamesene.
  • olefinic feedstocks comprising partially hydrogenated acyclic or cyclic Cio-C 30 conjugated hydrocarbon terpene (e.g., myrcene, ocimene, or famesene), wherein the partially hydrogenated hydrocarbon terpene comprises less than about 10% of the corresponding alkane and less than about 10% of the starting hydrocarbon terpene.
  • the partially hydrogenated hydrocarbon terpene comprises less than about 10% of the corresponding alkane and less than about 10% of the starting hydrocarbon terpene.
  • the partially hydrogenated hydrocarbon terpene e.g., myrcene, ocimene, or famesene
  • hydrogenated hydrocarbon terpene comprises about 5% or less (e.g., about 5%, 4%, 3%, 2% or 1%) of the corresponding alkane and about 5% or less of the starting hydrocarbon terpene.
  • an olefinic feedstock comprises about 5% or less (e.g., about 5%, 4%, 3%, 2%, 1% or less) famesene and about 5% or less (e.g., about 5%, 4%, 3%, 2%, 1%, or even less, e.g., an amount not detected by GC/MS) famesane, with the remainder being comprised of tetrahydrofamesene and hexahydrofamesene in any relative amounts.
  • partially hydrogenated famesene comprises less than about 10% famesene and less than about 10% famesane, such that the combined total of hexahydrofamesene and tetrahydrofamesene comprises at least about 80% of the partially hydrogenated farnesene (e.g., about 80%, about 85%, about 90%, about 95%, 96%, 97%, 98% or 99% of the partially hydrogenated farnesene), wherein any relative amounts of hexahydro farnesene and tetrahydrofamesene may be present.
  • the partially hydrogenated farnesene e.g., about 80%, about 85%, about 90%, about 95%, 96%, 97%, 98% or 99% of the partially hydrogenated farnesene
  • Some specific non-limiting examples of partially hydrogenated farnesene compositions wherein the combined total of hexahydrofarnesene and tetrahydrofamesene comprises about 80% of the total composition are provided in Table 2B below, where each "X" specifically discloses a feedstock comprising hexahydrofarnesene in the area% indicated on the horizontal axis and tetrahydrofamesene in the area% indicated on the vertical axis.
  • the amount of sulfur may be less than about lppm.
  • the amount of aromatic compounds may be less than about lppm.
  • the amount of sulfur and the amount of aromatic compounds may each be less than lppm.
  • the terpene is microbially derived from renewable carbon sources, and has a renewable carbon content of about 100%.
  • the amount of farnesene may be, individually, about 10%, 9%, 8%, 7%, 6%, 5%, 4%, 3%, 2%, 1%, 0.5%, 0.3%, or less than 0.3%, e.g., an amount not detectable by GC/MS.
  • the amount of famesane may be, individually, about 10%, 9%, 8%, 7%, 6%, 5%, 4%, 3%, 2%, 1%, 0.5%, 0.3%, or less than 0.3%, e.g., an amount not detectable by GC/MS.
  • a partially hydrogenated farnesene feedstock that is about 60-65% hydrogenated comprises about 40-50%
  • hexahydrofarnesene about 40-50% tetrahydrofamesene, less than about 10% dihydrofarnesene, less than about 1% (e.g., less than about 0.5% or no detectable amount by GC/MS) farnesane, and less than about 1% (e.g., less than about 0.5% or no detectable amount by GC/MS) farnesene.
  • a partially hydrogenated farnesene composition comprises substantial amounts of hexahydrofamesene and limited amounts of tetrahydrofamesene. It some situations, diolefinic species may contribute to undesired branching, cross-reactions, and the like. In some variations, limited amounts of tetrahydrofamesene present are substantially unconjugated, e.g., so that the composition comprises about 2% or less or about 1% or less conjugated diene.
  • compositions comprising substantial amounts of hexahydrofamesene and limited amounts of tetrahydrofamesene are provided in Table 2C below, where each "X" specifically discloses a feedstock comprising hexahydrofamesene in the area% indicated on the horizontal axis and tetrahydrofamesene in the area% indicated on the vertical axis.
  • the amount of sulfur may be less than about lppm.
  • the amount of aromatic compounds may be less than about lppm.
  • the amount of sulfur and the amount of aromatic compounds may each be less than lppm.
  • the terpene is microbially derived from renewable carbon sources, and has a renewable carbon content of about 100%.
  • the amount of farnesene may be, individually, about 10%, 9%, 8%, 7%, 6%, 5%, 4%, 3%, 2%, 1%, 0.5%, 0.3%, or less than 0.3%, e.g., an amount not detectable by GC/MS.
  • the amount of famesane may be, individually, about 10%, 9%, 8%, 7%, 6%, 5%, 4%, 3%, 2%, 1%, 0.5%, 0.3%, or less than 0.3%, e.g., an amount not detectable by GC/MS.
  • a suitable hydrocarbon terpene feedstock comprises about 70-85% mono- olefin, about 12-17% farnesane, and about 5% or less di-olefin. In some variations, a suitable hydrocarbon terpene feedstock comprises about 70-85% mono-olefin, about 12-17% farnesane, and about 3% or less di- olefin. In some variations, a suitable hydrocarbon terpene feedstock comprises about 70-85% mono-olefin, about 12-17% farnesane, and about 2% or less di-olefin.
  • a suitable hydrocarbon terpene feedstock comprises about 70-85% mono-olefin, about 12-17% farnesane, and about 1% or less di- olefin. In some variations, a suitable hydrocarbon terpene feedstock comprises about 75-85% mono-olefin, about 15% or less farnesane, and about 5% or less di-olefin. In some variations, a suitable hydrocarbon terpene feedstock comprises about 75-85% mono-olefin, about 15% or less farnesane, and about 3% or less di-olefin.
  • a suitable hydrocarbon terpene feedstock comprises about 75-85% mono- olefin, about 15% or less farnesane, and about 2% or less di-olefin. In some variations, a suitable hydrocarbon terpene feedstock comprises about 75-85% mono-olefin, about 15% or less farnesane, and about 1% or less di-olefin.
  • hydrocarbon terpenee is a hydrocarbon terpene other than farnesene, e.g., myrcene, springene, or geranylfarnesene.
  • one partially hydrogenated acyclic or cyclic conjugated C 10 -C30 hydrocarbon terpene as described herein is combined with one or more different partially hydrogenated acyclic or cyclic C 10 -C30 hydrocarbon terpenes as described herein to make a mixed olefinic feedstock.
  • a mixed olefinic feedstock may comprise partially hydrogenated myrcene mixed with partially hydrogenated farnesene. Any relative amounts of each of the partially hydrogenated terpenes are contemplated, and any relative degree of hydrogenation of each of the partially hydrogenated terpenes is contemplated.
  • mixed olefinic feedstocks are contemplated in which a ratio of a first partially hydrogenated hydrocarbon terpene to a second partially hydrogenated hydrocarbon terpene is about 0.1 : 1, 0.2: 1, 0.3: 1, 0.4: 1, 0.5: 1, 1 : 1, 2: 1, 3: 1, 4: 1, 5: 1, 6: 1, 7: 1, 8: 1, 9: 1 or 10: 1.
  • a mixed olefinic feedstock comprises one or more partially hydrogenated acyclic or cyclic C 10 -C30 hydrocarbon terpenes and one or more olefins not derived from an acyclic or cyclic C 10 -C30 hydrocarbon terpene.
  • the olefin may be selected from the group consisting of a C5-C30 linear alphaolefin, a C5-C30 branched alphaolefin, a C5-C30 linear internal olefin, and a C5-C30 branched internal olefin.
  • mixed olefinic feedstocks are contemplated in which a ratio of a partially hydrogenated hydrocarbon terpene to another olefin (e.g. , an alphaolefin) is about 0.1 : 1, 0.2: 1, 0.3: 1, 0.4: 1, 0.5: 1, 1 : 1, 2: 1, 3: 1, 4: 1, 5: 1, 6: 1, 7: 1, 8: 1, 9: 1 or 10: 1.
  • a ratio of a partially hydrogenated hydrocarbon terpene to another olefin e.g. , an alphaolefin
  • an additive is added to a hydrogenation catalyst to increase selectivity.
  • zirconium sulfate may be added to certain catalysts (e.g., palladium containing catalysts such as Pd/C) to increase selectivity.
  • a catalyst poison or additive is deliberately introduced to limit reactivity of a catalyst system and to increase selectivity. Any catalyst poison known in the art may be used in an effective amount.
  • Non-limiting examples of additives that may be used to limit reactivity of certain catalysts include triethylamine, carbon monoxide, pyridine, acetone, and ethylene diamine.
  • an acidic heterogeneous additive e.g., 3 ⁇ 40 5
  • the hydrocarbon terpene feedstock may be pre-treated (e.g., to remove oxygenates such as alcohols, acids, epoxides, or glycerides, or low boiling components).
  • pre-treatments to remove oxygenates from hydrocarbon terpene feedstock include distillation, filtration using silica or basic alumina, treatment using molecular sieves (e.g. 13X molecular sieves), or caustic washing (e.g., using 5-30% caustic) followed by centrifuge and separation of aqueous content.
  • a combination of two or more of caustic wash, filtration using alumina, and distillation is used to pre-treat hydrocarbon terpene feedstock. It should be noted that such pretreatment may occur prior to and/or following a partial hydrogenation step for the hydrocarbon terpene.
  • a hydrocarbon terpene feedstock is treated to remove oxygenates prior to partial hydrogenation (e.g., using silica or basic alumina), and is filtered using diatomaceous earth following partial hydrogenation.
  • a partially hydrogenated feedstock as described herein is stabilized by storing under an inert atmosphere (e.g., dry nitrogen) or by addition of an antioxidant such as 4-tert-butylcatechol (e.g., at 25-200ppm).
  • an antioxidant such as 4-tert-butylcatechol (e.g., at 25-200ppm).
  • a hydrocarbon terpene feedstock has a purity of greater than 97%, a farnesene dimer content of less than 3%, a water content measured by Karl Fischer titration of less than 400 ppm, and total acid number (TAN) of less than 0.1%.
  • a hydrocarbon terpene feedstock may include an antioxidant (e.g, TBC (4-tert-butyl catechol) of about 50-125 ppm. It should be noted that in the case of a partially hydrogenated feedstock, the hydrocarbon terpene may be pretreated prior to the selective hydrogenation process using any one of or any combination of the pre-treatments described herein or known in the art.
  • the presence of oxygenates or other contaminants may cause poisoning of catalyst or slow or unpredictable hydrogenation rates, so in some variations it may be desired to pre-treat a hydrocarbon terpene prior to the selective hydrogenation process.
  • the hydrocarbon terpene is not pre-treated to remove oxygenates or other contaminants prior to a selective hydrogenation process.
  • a specific species of partially hydrogenated conjugated hydrocarbon terpenes may or may not be produced by a hydrogenation process.
  • a partially hydrogenated hydrocarbon terpene species is prepared by a method that includes one or more steps in addition to or other than catalytic hydrogenation.
  • Nonlimiting examples of specific species partially hydrogenated conjugated hydrocarbon terpenes include any of the structures provided herein for dihydrofarnesene, tetrahydrofarnesene, and hexahydrofamesene; any of the structures provided herein for dihydromyrcene and tetrahydromyrcene; and any of the structures provided herein for dihydroocimene and tetrahydroocimene.
  • One example of a particular species of partially hydrogenated conjugated hydrocarbon terpene that may have utility as a feedstock is a terminal olefin having a saturated hydrocarbon tail with structure (AH):
  • n l, 2, 3, or 4.
  • a mono-olefinic alphaolefin having structure Al l may be derived from a conjugated hydrocarbon terpene wherein the conjugated diene is at the 1,3-position of the terpene.
  • alphaolefins derived from a 1,3-diene conjugated hydrocarbon terpene (e.g., a C10-C30 conjugated hydrocarbon terpene such as farnesene, myrcene, ocimene, springene, geranylfarnesene, neophytadiene, trans-p yia- 1,3 -diene, or czs-phyta- 1,3-diene).
  • a 1,3-diene conjugated hydrocarbon terpene e.g., a C10-C30 conjugated hydrocarbon terpene such as farnesene, myrcene, ocimene, springene, geranylfarnesene, neophytadiene, trans-p yia- 1,3 -diene, or czs-phyta- 1,3-diene.
  • a mono-olefinic alphaolefin having structure Al 1 may be prepared from the appropriate conjugated hydrocarbon terpene using any suitable method.
  • the mono-olefinic alphaolefin having structure Al 1 is produced from primary alcohol of corresponding to the hydrocarbon terpene (e.g., farnesol in the case of farnesene, or geraniol in the case of myrcene).
  • the methods comprise hydrogenating the primary alcohol, forming a carboxylic acid ester or carbamate ester from the hydrogenated alcohol, and pyrolizing the ester (or heating the ester to drive the elimination reaction) to form the alphaolefin with a saturated hydrocarbon tail, e.g., as described in Smith, L. E.; Rouault, G. F. J. Am. Chem. Soc. 1943, 65, 745-750 for the preparation of 3,7-dimethyloct-l-ene, which is incorporated by reference herein in its entirety.
  • the primary alcohol of the corresponding hydrocarbon terpene may be obtained using any suitable method. Examples 14 and 15 herein describe nonlimiting examples of methods for making an alphaolefin having structure A 12, 3,7, 1 1 -trimethyldodec- 1 -ene, from farnesol.
  • the hydrocarbon terpene has a conjugated diene at the 1,3-position, and the conjugated diene can be functionalized with any suitable protecting group known to one of skill in the art in a first step (which may comprise one reaction or more than one reaction).
  • the remaining olefinic bonds can be saturated in a second step (which may comprise one reaction or more than one reaction), and the protecting group can be eliminated to produce an alphaolefin having the general structure Al l in a third step (which may comprise one reaction or more than one reaction).
  • a hydrocarbon terpene having a 1,3-conjugated diene may be reacted with an amine (e.g., a dialkyl amine such as dimethylamine or diethylamine) in the first step to produce an amine having the formula N(Ri)(R 2 )(R 3 ), where Ri and R 2 are alkyl groups such as methyl or ethyl, and R 3 is an unsaturated d terpene.
  • an amine e.g., a dialkyl amine such as dimethylamine or diethylamine
  • N(Ri)(R 2 )(R 3 ) can be hydrogenated (e.g., using an appropriate catalyst), treated with peroxide, and heated to undergo elimination to form an alphaolefin having structure Al 1 (e.g., compound A12 if ⁇ -farnesene is used as the starting hydrocarbon terpene).
  • Scheme II illustrates this method using ⁇ -farnesene as a model compound.
  • a hydrogenated primary alcohol corresponding to a hydrocarbon terpene can be dehydrated using basic aluminum oxide (e.g., at a temperature of about 250°C) to make an alphaolefin having the general structure Al 1.
  • basic aluminum oxide e.g., at a temperature of about 250°C
  • Any suitable dehydration apparatus can be used, but in some variations, a hot tube reactor (e.g., at 250°C) is used to carry out a dehydration of a primary alcohol.
  • hydrogenated farnesol can be dehydrated using basic aluminum oxide (e.g., in a hot tube reactor at 250°C) to make compound A12, or an isomer thereof.
  • a mono-olefin having the general structure A13, A15 or Al l may in certain instances be derived from a conjugated hydrocarbon terpene having a 1,3-diene moiety, such as myrcene, farnesene, springene, geranylfarnesene, neophytadiene, trans-p yia- 1,3-diene, or cw-phyta- 1,3-diene.
  • the conjugated may be functionalized with a protecting group (e.g. , via a Diels-Alder reaction) in a first step, exocyclic olefmic bonds hydrogenated in a second step, and the protecting group eliminated in a third step.
  • a conjugated hydrocarbon terpene having a 1,3-diene is reacted with S0 2 in the presence of a catalyst to form a Diels-Alder adduct.
  • the Diels-Alder adduct may be hydrogenated with an appropriate hydrogenation catalyst to saturate exocyclic olefmic bonds.
  • a retro Diels-Alder reaction may be carried out on hydrogenated adduct (e.g., by heating, and in some instances in the presence of an appropriate catalyst) to eliminate the sulfone to form a 1,3-diene.
  • the 1,3-diene can then be selectively hydrogenated using a catalyst known in the art to result in a mono-olefin having structure Al 1, A13 or A15, or a mixture of two or more of the foregoing.
  • a catalyst known in the art to result in a mono-olefin having structure Al 1, A13 or A15, or a mixture of two or more of the foregoing.
  • Non-limiting examples of regioselective hydrogenation catalysts for 1,3-dienes are provided in Jong Tae Lee et al, "Regioselective hydrogenation of conjugated dienes catalyzed by hydridopentacyanocobaltate anion using ⁇ -cyclodextrin as the phase transfer agent and lanthanide halides as promoters," J. Org. Chem., 1990, 55 (6), pp. 1854-1856; in V. M.
  • ⁇ -farnesene can be reacted with SO 2 in the presence of a catalyst to form a Diels-Alder adduct, which is subsequently hydrogenated, and the sulfone eliminated to form a 1,3-diene, which is subsequently selectively hydrogenated using a catalyst known in the art for regioselective hydrogen additions to 1,3-dienes to form 3,7,1 1 -trimethyldodec-2-ene, 3,7,1 1- trimethyldodec- 1 -ene, or 3-methylene-7,l 1 -dimethyldodecane, or a mixture of any two or more of the foregoing.
  • a terminal olefin of the general structure A14 may be made from a conjugated hydrocarbon terpene having a 1,3 -conjugated diene and at least one additional olefinic bond (e.g., myrcene, farnesene, springene, or geranylfarnesene):
  • a compound having the structure A14 may be derived from an unsaturated primary alcohol corresponding to the relevant hydrocarbon terpene (e.g., farnesol in the case of farnesene, or geraniol in the case of myrcene).
  • the unsaturated primary alcohol may be exposed to a suitable catalyst under suitable reaction conditions to dehydrate the primary alcohol to form the terminal olefin A14.
  • a stochiometric deoxygenation-reduction reaction may be conducted to form compounds having structure A14 from a primary alcohol (e.g., farnesol or geraniol) of a hydrocarbon terpene.
  • a primary alcohol e.g., farnesol or geraniol
  • One prophetic example of such a reaction can be conducted according to a procedure described in Dieguez et al., "Weakening C-0 Bonds: Ti(III), a New Regaent for Alcohol Deoxygenation and Carbonyl Coupling Olefination," J. Am. Chem. Soc. 2010, vol. 132, pp.
  • a mixture of titanocene dichloride ( ⁇ 5 - C 5 H 5 ) 2 TiCl 2 (Cp 2 TiCl 2 ) (3.88 mmol) and Mn dust (2.77 mmol) in strictly deoxygenated tetrahyrofuran (THF) (7 mL) can be heated at reflux under stirring until the red solution turns green. Then, to this mixture can be added a solution of the primary alcohol (e.g., farnesol or geraniol) (1.85 mmol) in strictly deoxygenated THF (4 mL).
  • the primary alcohol e.g., farnesol or geraniol
  • reaction can be quenched with IN HC1 and extracted with tert-butylmethyl ether (t-BuOMe).
  • t-BuOMe tert-butylmethyl ether
  • the organic phase can be washed with brine, filtered and concentrated in vacuo to yield a crude product, which can be purified, e.g., by column chromatography (hexane/t-BuOMe, 8: 1) over silica gel column to afford a compound having structure A14 (e.g., 3,7,1 1 -trimethyldodeca- 1,6,10-triene if farnesol is used as the starting material).
  • the resulting crude may be purified, e.g., by column chromatography (hexane/t-BuOMe, 8: 1) on silica gel to afford compound having structure A14 (e.g., 3,7, 11- trimethyldodeca- 1 ,6, 10-triene if farnesol is used as the starting material).
  • column chromatography hexane/t-BuOMe, 8: 1
  • silica gel e.g., 3,7, 11- trimethyldodeca- 1 ,6, 10-triene if farnesol is used as the starting material.
  • An olefinic feedstock as described herein may comprise any useful amount of the particular species (e.g., alphaolefinic species having structure Al l, A12 or A15, mono-olefinic species having structure A13, or unsaturated terminal olefin species having structure A 14), made either by a partial hydrogenation route or by another route, e.g., as described herein.
  • alphaolefinic species having structure Al l, A12 or A15 mono-olefinic species having structure A13, or unsaturated terminal olefin species having structure A 14
  • an olefinic feedstock comprises at least about 1%, at least about 5%, at least about 10%, at least about 20%, at least about 30%, at least about 40%, at least about 50%, at least about 60%, at least about 70%, at least about 80%, or at least about 90% species having structure Al l, A12, A13, A14, or A15.
  • an olefinic feedstock comprises at least about 1%, at least about 5%, at least about 10%, at least about 20%, at least about 30%, at least about 40%, at least about 50%, at least about 60%, at least about 70%, at least about 80%, or at least about 90% 3,7,1 1-trimethyldodec-l-ene.
  • an olefinic feedstock comprises at least about 1%, at least about 5%, at least about 10%, at least about 20%, at least about 30%, at least about 40%, at least about 50%, at least about 60%, at least about 70%, at least about 80%, or at least about 90% 3 -methylene- 7, 1 1 -dimethyldodecane.
  • an olefinic feedstock comprises at least about 1%, at least about 5%, at least about 10%, at least about 20%, at least about 30%, at least about 40%, at least about 50%, at least about 60%, at least about 70%, at least about 80%, or at least about 90% 3,7,1 1 -trimethyldodec-2-ene.
  • an olefinic feedstock comprises at least about 1%, at least about 5%, at least about 10%, at least about 20%, at least about 30%, at least about 40%, at least about 50%, at least about 60%, at least about 70%, at least about 80%, or at least about 90% 3,7, 1 1 -trimethyldodeca- 1,6, 10-triene.
  • an olefinic feedstock comprises at least about 1%, at least about 5%, at least about 10%, at least about 20%, at least about 30%, at least about 40%, at least about 50%, at least about 60%, at least about 70%, at least about 80%, or at least about 90% 3,7- dimethyloct- 1 -ene.
  • an olefinic feedstock comprises at least about 1%, at least about 5%, at least about 10%, at least about 20%, at least about 30%, at least about 40%, at least about 50%, at least about 60%, at least about 70%, at least about 80%, or at least about 90% 3,7-dimethyloct-2-ene. In certain variations, an olefinic feedstock comprises at least about 1%, at least about 5%, at least about 10%, at least about 20%, at least about 30%, at least about 40%, at least about 50%, at least about 60%, at least about 70%, at least about 80%, or at least about 90% 3,7-dimethylocta-l,6-diene.
  • the alphaolefinic species of the conjugated hydrocarbon terpenes may be used as substitutes for, or as supplements to (e.g., in a co-feed configuration) conventional linear alphaolefins or branched alphaolefins in any industrial process known to utilize such alphaolefins, e.g. , oligomerization utilizing alphaolefins, polymerization utilizing alphaolefins, hydroformylation utilizing alphaolefins, or carbonylation utilizing alphaolefins.
  • the internal olefins species may be used as substitutes for, or as supplements to (e.g., in a co-feed configuration) conventional internal olefins in any industrial process known to utilize such internal olefins, e.g., oligomerization using internal olefins, polymerization using internal olefins, hydroformylation using internal olefins, or carbonylation using internal olefins.
  • the olefinic feedstocks comprising alphaolefinic species or internal olefinic species of partially hydrogenated hydrocarbon terpenes are suitable for catalytic reaction with one or more alphaolefins to form a mixture of isoparaffins comprising adducts of the terpene and the one or more alphaolefins.
  • at least a portion of the mixture of isoparaffins so produced may be used as a base oil.
  • the olefinic feedstocks comprising alphaolefinic species or internal olefinic species of partially hydrogenated hydrocarbon terpenes may be used to produce products such as alcohols, detergents, surfactants, polymers, plastics, rubbers, or oils.
  • Example 1 Preparation of 60% hydrogenated ⁇ -farnesene containing no detectable amount of ⁇ - farnesene and no detectable amount of farnesane
  • ⁇ -farnesene was filtered through activated alumina. 20 mL of the alumina filtered ⁇ -farnesene was put into a reactor with 25mg of 0.3wt% ⁇ 7 ⁇ 1 2 ⁇ 3 (available from Johnson Matthey, PRICAT 309/7, 0.3% Pd/Alumina Trilobe 2.5mm) that had been ground from pellets. The slurry so formed was stirred at about lOOOrpm. The reactor was heated to about 100°C. The reactor was pressurized to about 100 psig, and approximately 3 molar equivalents of hydrogen were delivered to the reactor (including auxiliary plumbing). The reaction was allowed to proceed for several hours.
  • ⁇ -farnesene was hydrogenated to about 60% as described in Example 1 in a first stage, except that the ⁇ -farnesene was not treated with alumina prior to use, 1 OOmg of 0.3wt% Pu7Al 2 03 was used per 20 mL farnesene, and the reaction temperature was 160°C.
  • the reactor was heated to a higher temperature (200°C for Example 2, 220°C for Example 3, 240°C for Example 4, and 260°C for Example 5), and the hydrogen pressure was decreased to about 20 psig in reactor pressure.
  • composition of each of the partially hydrogenated products was analyzed by GC-MS and by GC/FID.
  • Conditions for the GC-MS were as follows: Agilent 6890 GC, Column Agilent HP- 1, 50m x 0.2mm, 0.1 lOmicron film, P/N 19091Z-005, Agilent 5973 Mass Selective Detector, oven ramp from 50°C to 320°C, inlet in split mode (50: 1 split ratio), helium as carrier gas, hexane as diluent, trans-ft-farnesene or farnesane used as reference.
  • Analysis of the composition of each of the products by GC/FID is as follows.
  • An Agilent model 7890 GC having a flame ionization detector is used.
  • a sample of partially hydrogenated farnesene is dissolved in n-heptane (at about lmg/mL) containing 100 ⁇ g/mL n-hexadecane that serves as a retention time reference.
  • An Agilent model DB-17ms GC column (60m, 0.25mm, 0.25micron) is used that is made from 50% phenyl- and 50% methyl-polysiloxane.
  • inlet type is multi-mode or split-splitless, a split ratio 1 :20 is used, a constant pressure of about 10.64 psi is used, inlet temperature is 250°C, flow rate is about 0.597 mL/min, carrier gas is hydrogen, injection volume is 1 microliter, the oven is set to have an initial temperature of 150°C, a run time of 20 minutes is used.
  • the phenyl component in the column gives the stationary phase the ability to interact with the pi-electrons of the various double -bonds of the partially hydrogenated farnesene species.
  • the GC-FID is used to quantify the weight contribution of each molecular weight constituent peak, proportional to the peak's area percent.
  • each peak is given a unique name, an area of 1.0, and an amount corresponding to the molecular mass of the peak shown in Table 3.
  • the n-hexadecane is given an amount of 1.0, an area of 1.0 and a multiplier of a very small number, e.g., lxlO 0 , and n-hexadecane is set as the only time reference peak.
  • the calculation proceeds as follows. The sample is injected, separated by the column and detected. Peak areas are integrated and identified with the appropriate mass.
  • the calibration report is set-up to multiply each peak's area percent times the calibration factor (amt/area) (the molecular mass).
  • the resulting sum of amounts is reported as a number between 204 and 212, which represents the average molecular mass.
  • the values for each mass level (204 to 212) are summed and divided by the overall sum to obtain and report the fraction for each mass level: Farnesane has a mass level of 212,
  • hexahydrofarnesene has a mass level of 210
  • tetrahydrofarnesene has a mass level of 208
  • dihydrofarnesene has a mass level of 206, and farnesene (and its isomers) has a mass level of 204.
  • the n- hexadecane is identified, but its amount contribution is very small and negligible.
  • the peak area percent contributions for each molecular weight are summed and the average molecular weight of the entire sample is calculated to provide degree of hydrogenation. Results for Examples 2-5 are provided in Table 4, with compositional results measured by GC-MS and GC-FID both shown (GC-FID results in parentheses).
  • the instant example provides a partially hydrogenated mono-olefmic famesene feedstock prepared according to the staged hydrogenation methods described above.
  • the reactor was pressurized to 970 psig with hydrogen gas.
  • the 970 psig hydrogen gas corresponded to about 0.5 molar equivalents of hydrogen.
  • another pulse of hydrogen was added to pressurize the reactor to 970 psig.
  • a total of 6 pulses of hydrogen were added to the reactor in this manner, with the first two pulses auto-heating the reactor to about 40°C-50°C.
  • the reactor was heated to about 140°C to complete the consumption of the hydrogen.
  • the reactor was heated to about 140°C.
  • the slurry was removed from the reactor.
  • the catalyst was removed from the slurry by filtration through silica gel, yielding 453.4 of partially hydrogenated farnesene characterized by GC-MS as described for Example 2, except that the samples were diluted in ethyl acetate, as shown in FIG. 1.
  • the bromine index of the partially hydrogenated farnesene was measured according to ASTM 2710 using a titrant strength of 0.02 M bromide -bromate, and indicated the sample was 71% hydrogenated.
  • the farnesane content in the hydrogenated sample was measured to be 5% by GC-MS, based on the total hydrogenated sample.
  • the GC-MS spectrum showed no detectable amount of farnesene or dihydrofarnesene.
  • the area percents of hexahydrofarnesene and tetrahydrofarnesene in the hydrogenated sample were calculated algebraically using the % hydrogenation in the total sample determined from the measured bromine index and the measured area% for the saturated component. Results are summarized in Table 4. The area % farnesane is measured to within +/- 2%, and the area% of hexahydrofarnesene and tetrahyrofarnesene are measured to within +/-4% accuracy.
  • the instant example provides another example of a mono-olefinic farnesene feedstock prepared according to the methods described herein.
  • Example 7 was prepared and analyzed as in Example 6.
  • FIG. 2 shows the GC-MS spectrum for Example 7. Results are summarized in Table 4.
  • the instant example provides a dihydrofarnesene feedstock prepared according to the methods described herein.
  • Example 8 was carried out as in Example 6, except that only two pulses of hydrogen gas (corresponding to a total of one molar equivalent) were delivered to the reactor. The results were analyzed by GC-MS and NMR. A l H NMR spectrum of the product is shown in FIG. 3. By NMR and GC-MS, the reaction product included the following species in the indicated molar percents:
  • Example 9 Alternate preparation of a 25% hydrogenated olefinic feedstock from ⁇ -farnesene
  • the instant example provides another example of a dihydrofarnesene feedstock prepared according to the methods described herein.
  • ⁇ -farnesene (26.0 g, 0.127 mol) and 0.26 g of Lindlar's catalyst (5% Pd/Pb on CaC0 3 , available from Sigma Aldrich) were placed in a 100 mL autoclave.
  • the apparatus was evacuated/flushed with N 2 three times and then charged with one equivalent of hydrogen (690 psig). The mixture was stirred (500 rpm) at 19 °C for 18 hours.
  • the catalyst was removed by filtration to afford 25.8 g (98.5%) of a mixture of the following five compounds, with their corresponding molecular ion weights.
  • Example 10 Preparation of 75% hydrogenated olefinic feedstock from ⁇ -farnesene using single stage controlled hydrogenation
  • the instant example provides an additional example of a mono-olefmic farnesene feedstock prepared according to the methods described herein.
  • a catalyst (5wt% Pd/C, available from Strem Chemicals, as described in Example 6 above) was immersed into ⁇ -farnesene (Amyris, as described in Example 6) to form a slurry in a closed reactor at a loading of 3. lg/kg liquid. The slurry was agitated. The reactor was purged with nitrogen using 3 pressure/vacuum cycles, pressuring to 100 psig with nitrogen and evacuating to 3 or less psia in each cycle. After the third cycle, the reactor was left under 3 or less psia nitrogen, and agitation was stopped. The reactor was pressurized to 50 psig with hydrogen and allowed to stabilize.
  • the partially hydrogenated farnesene was analyzed using GC-FID and GC-MS using an Agilent DB-17ms 60m column as described above for Examples 2-5, and was also characterized by GC-MS using an HP-1 50 m long x 200 micron ID x 1 10 nm film thickness column and using hexane as a solvent as described for Example 2.
  • GC-FID results are shown in parentheses. Poorer resolution of peaks was achieved using the 50m column, leading to increased need for splitting overlapping areas. Peak areas corresponding to each of farnesene, farnesane, dihydrofarnesene, tetrahydrofarnesene, and hexahydrofarnesene were determined to result in the species distribution as shown in Table 5.
  • the sample was calculated to have an average molecular weight of 210.0 by GC-FID, corresponding to 75% hydrogenated.
  • the Bromine number of the sample was measured according to ASTM Dl 159 to be 80.6, and is estimated to be 76 if the substance responds to bromine as a triunsaturate (refer to Table 1).
  • Example 11 Preparation of 78% hydrogenated olefinic feedstock from ⁇ -farnesene using single stage controlled partial hydrogenation [00229]
  • the instant example provides an additional example of a mono-olefmic farnesene feedstock prepared according to the methods described herein.
  • Example 1 1 was carried out as in Example 10, except that 3.1 molar equivalents of hydrogen were consumed during the reaction, and a catalyst loading of 2. lg/kg was used.
  • the partially hydrogenated farnesene was analyzed using GC-FID and GC-MS as described for Example 10. Results are shown in Table 5.
  • the sample was calculated to have an average molecular weight of 210.3 by GC- FID, corresponding to 78% hydrogenated.
  • the Bromine number of the sample by GC- was measured according to ASTM Dl 159 to be 71.9, and is estimated to be 65.9 if the substance responds to bromine as a triunsaturate (refer to Table 1).
  • the instant example provides an additional example of a farnesene feedstock comprising predominantly di-olefins and mono-olefins prepared according to the methods described herein.
  • Example 12 was carried out as in Example 10, except that 2.5 molar equivalents of hydrogen were consumed during the reaction, and a catalyst loading of 2. lg/kg was used.
  • the partially hydrogenated farnesene was analyzed using GC-MS as described for Example 10. Results are shown in Table 5.
  • the sample was calculated to have an average molecular weight of 209.3 by GC-FID, corresponding to 67% hydrogenated.
  • the Bromine number of the sample was measured according to ASTM Dl 159 to be 1 12.9, and is estimated to be 109.2 if the substance responds to bromine as a triunsaturate (refer to Table 1).
  • the instant example provides an additional example of a mono-olefmic farnesene feedstock prepared according to the methods described herein.
  • Example 13 was carried out as in Example 10, except that 3.35 molar equivalents of hydrogen were consumed during the reaction, and a catalyst loading of 2. lg/kg was used.
  • the partially hydrogenated farnesene was analyzed using GC-MS as described for Example 10. Results are shown in Table 5.
  • the sample was calculated to have an average molecular weight of 210.8 by GC-FID, corresponding to 85% hydrogenated.
  • the Bromine number of the sample was measured according to ASTM Dl 159 to be 52.7, and is estimated to be 49.2 if the substance responds to bromine as a triunsaturate (refer to Table 1).
  • the instant example provides an example of an alphaolefin prepared according to the methods described herein.
  • Example 15 provides an alternate synthesis (Method B) of 3,7,1 1-trimethyldodec-l-ene from farnesol.
  • step a) of Method B 3,7,1 1 -trimethyl- 1 -decanol (Compound 2, as prepared in Example 9 above) is reacted with diphenylcarbamoyl chloride (Compound 7 below, available from Sigma Aldrich) to form 3,7,1 1 -trimethyl- 1 -dodecyl-N,N-diphenylcarbamate (Compound 8 below).
  • step b) of Method B Compound 8 is is prepared from Compound 8.
  • Example 16 For each of Examples 16-31 , a 1 -Liter reactor with an H 2 reservoir was charged with 660 mL ⁇ -farnesene as described in Example 6. Catalyst as specified in Table 5 was mixed into the farnesene and the reactor was stirred at 1000 rpm, except Example 16, which was stirred at 500 rpm. After purging as described in Example 6, the reactor was pressurized with hydrogen to 100 psig (external). The reactor was allowed to self-heat as provided in Table 6, and then heated using an external heater to a first stage reaction temperature of 100°C. After a decline in hydrogenation rate to near zero indicated the 1.5 equivalents of hydrogen had been consumed, the temperature was increased in a second stage as shown in Table 6.
  • hydrogen pressure in the second stage was the same as in the first stage (100 psig).
  • hydrogen pressure in the second stage was lowered relative to the first stage, as shown in Table 6.
  • the hydrogen pressure was initially reduced to 10 psig in the second stage after 1.5 equivalents hydrogen were consumed, then increased to 20 psig after 2.3 equivalents hydrogen were consumed, and increased again to 30 psig after 2.9 equivalents hydrogen were consumed.
  • Example 16-26, 28-29, and 31 0.3 wt% Pd/A1203 was supplied by Johnson Matthey (Type 335, powder, size D50:45).
  • Example 27 5 wt% Pd/C as in Example 6 is used.
  • Examples, 23-27, and 29-31 a catalyst loading of 18ppm Pd in farnesene was used.
  • Example 28 a catalyst of 14 ppm Pd in farnesene was used.
  • FIG. 4A illustrates the temperature and specific hydrogenation rate ( ⁇ H 2 /min/g- farnesene) for the hydrogenation process of Example 23.
  • hydrogen pressure is 100 psig in the first and second stages.
  • FIG. 4B illustrates the temperature and specific hydrogenation rate for the hydrogenation process of Example 25.
  • hydrogen pressure is 100 psig in the first stage, and is reduced to 10 psig in the second stage.
  • Table 6 provides total equivalents of hydrogen consumed, run time, % mono-olefin, % di- olefin, % tri-olefin, and % farnesane for each of Examples 16-31.
  • the relative quantities of the species were measured by GC-FID as described above for Example 2.
  • the amount of tetra-olefin present was negligible. Results are plotted in FIGS. 5A-5F.
  • % mono-olefin is increased while % di-olefin is reduced by increasing temperature in the second stage and reducing pressure in the second stage.
  • a composition comprising 75% or greater (in some cases 80% or greater) mono-olefin and 5% or less di-olefin is achieved using a second stage temperature of 210-240°C and a second stage pressure of 10 psig.
  • Example 16 The effect of pretreatment of ⁇ -farnesene to remove oxygenates and other polar substances was investigated.
  • the ⁇ -farnesene was filtered with silica gel (1.1 L farnesene/400ml silica gel).
  • the ⁇ -farnesene was filtered with basic alumina (0.9 kg farnesene/0.45 kg alumina basic, standard activity 1).
  • the ⁇ -farnesene was treated by mixing with 0.45 kg SelexorbTM CDX 1/8" and stirred 1 hour.
  • Example 20 the ⁇ -farnesene was treated with caustic, washed with water, and treated with Celite.
  • Example 21 the ⁇ -farnesene was treated with 1 wt% NaOH beads.
  • Example 22 the ⁇ -farnesene was treated with 0.2 wt% NaOH.
  • Example 23-30 the ⁇ -farnesene had been redistilled and filtered through basic alumina prior to use.
  • Example 31 the ⁇ -farnesene was not pretreated. The untreated farnesene exhibited very slow hydrogenation rates. Specific hydrogenation rates were measured after 2 equivalents of hydrogen had been consumed: Example 16 (silica gel treatment), specific hydrogenation rate of 400 ⁇ H 2 /min/g-farnesene; Example 17 (basic alumina treatment), specific hydrogenation rate of 1200 ⁇ H 2 /min/g-farnesene; Example 19
  • Example 20 (SelexorbTM treatment), specific hydrogenation rate of 600 ⁇ H 2 /min/g-farnesene;
  • Example 20 (caustic-water treatment), specific hydrogenation rate of 210 ⁇ H 2 /min/g-farnesene;
  • Example 21 (1 wt% NaOH bead treatment), specific hydrogenation rate of 400 ⁇ H 2 /min/g-farnesene;
  • Example 22 (0.2 wt% NaOH bead treatment), specific hydrogenation rate of 400 ⁇ H 2 /min/g-farnesene.
  • Example 32 Staged hydrogenation in a fixed bed reactor
  • the feed was 25vol/vol% ⁇ -farnesene in Durasyn® 164 PAO fluid, ⁇ -farnesene was supplied by Amyris (>97% pure) and received no further pretreatment before use. Pure hydrogen (no nitrogen diluent) was used.
  • Each reactor was operated in trickle flow mode and configured to have two hydrogenation zones. A first (top) hydrogenation zone begins at the inlet and extends for the top to a maximum distance of 6cm, depending on quantity of catalyst in the first zone. Each reactor is packed with catalyst in the first zone and is heated to maintain a temperature of 120°C.
  • the second (bottom) hydrogenation zone begins below the unheated intermediate zone and extends downward for 2-14 cm (depending on quantity of catalyst in second zone), is packed with catalyst and heated to maintain a temperature of 225°C.
  • the bottom two centimeters of the reactor are heated to 225°C and are packed with inert Zirblast® ceramic beads with no catalyst.
  • a diagram of the reactors is shown in FIG. 6. A factorial design was set up to result in 16 different combinations of top and bottom catalyst loadings as shown in Table 7A.
  • the reaction was operated with a liquid hourly space velocity (LHSV) of 5-55 g-feed/g- catalyst/hour (x 1 ⁇ 4 for farnesene LHSV) and gas hourly space velocity (GHSV) of 330-3000 Nml/g- catalyst/hour. Hydrogen was supplied in excess at 20-30%. Outlet pressure was 1 atmosphere. Liquid and gas flow rates are adjusted to limit hydrogenation at about 75% if possible.
  • LHSV liquid hourly space velocity
  • GHSV gas hourly space velocity
  • Reactors neighboring blocked reactors (2, 4, 10, and 12) were impacted by the blocked reactors.
  • the degree of hydrogenation was less than 40%.
  • Reactors having both top and bottom catalysts can achieve mono-olefin greater than 80% as long as activity is controlled to inhibit excess formation of farnesane.
  • Reactors 3, 6, 7, 8, 1 1, 14, 15, 16 were running at 24 mg/min 25vol% farnesene in Durasyn®, 45 Nml/min H 2 , 40 and 35 Nml/min H 2 , and a pressure drop less than 5 barg.
  • Reactor 1 1 experienced pressure oscillations.
  • Reactors 8 and 11 resulted in a degree of hydrogenation that was greater than 80%.
  • Reactors 3, 6, and 7 are measured under optimized conditions, and detailed experimental conditions and results are provided in Table 7B. Stable operation for these reactors was observed over 500 h.
  • the catalyst could be reactivated at 250°C under hydrogen.
  • mono-olefin content (as measured by GC) ranged from about 79- 81%
  • di-olefin content ranged from 1 1%-2%
  • farnesane ranged from 8- 18%.
  • Parameters for the GC- MS measurement are as follows. A Thermo Trace-GC with FID detection and DSQ II mass spectroscopy with electric ionization is used.
  • the column type is VF-WaxMS 0.25mm x 0.25 micron x 30m.
  • the start temperature is 60°C and the hold time is 0 minute.
  • the temperature is ramped to 150°C at a rate of 6°C/min. and held for 6 minutes, and then ramped to 250°C at 30°C/min and held for 2 minutes.
  • the injection temperature is 250°C.
  • Split flow at 200 mL/min is used.
  • FID temperature is 275°C.
  • the injection volume is 0.5 microliters. Mono-olefms (molecular weight of 210) are observed with retention times at 5.95-6.15, 6.25-7.03, and 7.15 minutes.
  • Di-olefins (molecular weight of 208) are observed with retention times at 7.06 and 7.2-8.35 minutes.
  • Tri-olefins (molecular weight of 206) are observed with retention times at 8.35-9.3 minutes.
  • Tetra-olefins (molecular weight of 204) are observed with retention times of 9.4-9.6 minutes.
  • Farnesane (MW 212) is observed with a retention time of 6.2 minutes.
  • Parameters for GC-FID are as follows. A Thermo Trace-GC with FID detection is used.
  • the column type is VF-WaxMS 0.25mm x 0.25 micron x 30m.
  • the start temperature is 80°C, with a hold time of 0 minutes.
  • the temperature is ramped to 140oC with a hold time of 0 minutes.
  • Split flow at 80 mL/min is used.
  • the injection temperature is 250oC.
  • the carrier flow rate is 2 mL/min.
  • the FID temperature is 270°C.
  • the injection volume is 0.2 microliters.
  • Mono-olefms are observed with retention times of 5.62- 7.02 minutes, di-olefins are observed with retention times of 7.02-9.18 minutes, tri-olefins are observed with retention times of 9.18-1 1.45 minutes, farnesane is observed at 5.04 minutes with a window of 0.15, tetra-olefins are observed at a retention time of 1 1.92 minutes with a window of 0.5, and farnesol is observed with a retention time of 13.5 minutes with a window of 0.2.
  • Example 33 Effect of hydrogen pressure on selectivity.
  • the refractive index of farnesene is approximately 1.4880 and a sample having a degree of hydrogenation of 30% has a refractive index of approximately 1.4700.
  • the composition of the 23.5% hydrogenated ⁇ -farnesene is 0.1% farnesane, 0.7% mono-olefin, 2.8% di-olefin, 86.3% tri-olefm, and 10.1% farnesene by GC-FID.
  • the 23.5% hydrogenated farnesene was distilled and treated with 10wt% AI 2 O 3 and 10wt% silica.
  • 20g of the pretreated 25% hydrogenated farnesene is loaded into a reactor with 400mg 0.3 wt% Pd/Al 2 0 3 (Johnson Matthey 309/7).
  • the reactor is stirred at 1200rpm.
  • the temperature of the reactor was set to 200°C.
  • the hydrogen pressure was set to about 30 psig.
  • the reaction was allowed to proceed until a total of about 3 equivalents hydrogen were consumed, including the 0.94 equivalents from the first stage.
  • the experiment was repeated for hydrogen pressures of 50, 70, 90 and 1 10 psig.
  • Results are shown in Table 8, where % of each species is determined by GC-FID as described in Example 2. Using a degree of hydrogenation of slightly less than 75%, a second stage hydrogen pressure of 50 psig and a second stage temperature of 200°C, a composition comprising 85% mono-olefin, ⁇ 1% di-olefin, and ⁇ 15% farnesane is achieved. Table 8
  • Example 34 Monitoring population of species during hydrogenation.
  • a first hydrogenation stage is carried out as in Example 33, except that about 30-40% hydrogenation is accomplished in the first stage.
  • Three different second stage hydrogenations are carried out with the temperature being 200°C, with the hydrogen pressure being 2 bar, 1 bar, or 0.5 bar.
  • Samples are taken as the hydrogenation proceeds and species are analyzed as described in Example 32. Results are shown in FIGS 7A-7C.
  • Second stage hydrogenation conditions for the data shown in FIG. 7A are 200°C, 2 bar hydrogen pressure;
  • second stage hydrogenation conditions for the data shown in FIG. 7B are 200°C, 1 bar hydrogen pressure;
  • second stage hydrogenation conditions for the data shown in FIG. 7C are 200°C, 0.5 bar hydrogen pressure.
  • X represents farnesene content
  • solid squares represent mono-olefin content
  • solid triangles represent di-olefin content
  • solid diamonds represent farnesane content.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Lubricants (AREA)
  • Detergent Compositions (AREA)

Abstract

L'invention concerne des charges d'alimentation oléfiniques dérivées de terpènes hydrocarbonés conjugués (par exemple, terpènes en C10-C30), leurs procédés de fabrication, et leurs procédés d'utilisation.
PCT/US2012/024922 2011-04-13 2012-02-13 Oléfines et procédés de fabrication desdites oléfines WO2012141783A1 (fr)

Priority Applications (6)

Application Number Priority Date Filing Date Title
BR112013026417-9A BR112013026417B1 (pt) 2011-04-13 2012-02-13 Olefinas e métodos para produção destas
US14/112,235 US10294439B2 (en) 2011-04-13 2012-02-13 Olefins and methods for making the same
EP12708189.1A EP2697187B1 (fr) 2011-04-13 2012-02-13 Oléfines et procédés de fabrication desdites oléfines
US16/389,690 US11193078B2 (en) 2011-04-13 2019-04-19 Olefins and methods for making the same
US17/518,540 US11802100B2 (en) 2011-04-13 2021-11-03 Olefins and methods for making the same
US18/371,412 US20240043356A1 (en) 2011-04-13 2023-09-21 Olefins and methods for making the same

Applications Claiming Priority (12)

Application Number Priority Date Filing Date Title
US201161475221P 2011-04-13 2011-04-13
US201161475217P 2011-04-13 2011-04-13
US61/475,221 2011-04-13
US61/475,217 2011-04-13
US201161482122P 2011-05-03 2011-05-03
US61/482,122 2011-05-03
US201161493316P 2011-06-03 2011-06-03
US61/493,316 2011-06-03
US201161502252P 2011-06-28 2011-06-28
US61/502,252 2011-06-28
US201161524143P 2011-08-16 2011-08-16
US61/524,143 2011-08-16

Related Child Applications (2)

Application Number Title Priority Date Filing Date
US14/112,235 A-371-Of-International US10294439B2 (en) 2011-04-13 2012-02-13 Olefins and methods for making the same
US16/389,690 Division US11193078B2 (en) 2011-04-13 2019-04-19 Olefins and methods for making the same

Publications (2)

Publication Number Publication Date
WO2012141783A1 true WO2012141783A1 (fr) 2012-10-18
WO2012141783A4 WO2012141783A4 (fr) 2012-12-20

Family

ID=45787337

Family Applications (2)

Application Number Title Priority Date Filing Date
PCT/US2012/024922 WO2012141783A1 (fr) 2011-04-13 2012-02-13 Oléfines et procédés de fabrication desdites oléfines
PCT/US2012/024926 WO2012141784A1 (fr) 2011-04-13 2012-02-13 Huiles de base et leurs procédés de production

Family Applications After (1)

Application Number Title Priority Date Filing Date
PCT/US2012/024926 WO2012141784A1 (fr) 2011-04-13 2012-02-13 Huiles de base et leurs procédés de production

Country Status (5)

Country Link
US (5) US10294439B2 (fr)
EP (2) EP2697187B1 (fr)
BR (2) BR112013026416B1 (fr)
PT (1) PT2697187T (fr)
WO (2) WO2012141783A1 (fr)

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2015168658A1 (fr) * 2014-05-02 2015-11-05 Amyris, Inc. Compositions de solvant à base de dihydrofarnésène
CN105122380A (zh) * 2013-02-21 2015-12-02 Abb技术有限公司 可再生烃基绝缘流体
WO2016064853A1 (fr) * 2014-10-20 2016-04-28 Novvi Llc Hydrogénation partielle sélective de bêta-farnesène
WO2016177868A1 (fr) 2015-05-07 2016-11-10 Total Marketing Services Hydrogénation partielle sélective de terpènes à l'aide d'un catalyseur à base de nickel
WO2016177866A1 (fr) * 2015-05-07 2016-11-10 Total Marketing Services Hydrogénation sélective de terpènes à l'aide d'un catalyseur à base d'iridium
WO2017059136A1 (fr) * 2015-10-02 2017-04-06 Amyris, Inc. Compositions contenant du farnesène à base de biomatériau ou composés dérivés de celui-ci et leur utilisation dans des produits de consommation et industriels
CN107153091A (zh) * 2017-05-31 2017-09-12 中国科学院地球化学研究所 植物同化铵盐的无机氮同位素分馏值的测定方法
US9862906B2 (en) 2011-04-13 2018-01-09 Amyris, Inc. Base oils and methods for making the same
US11208607B2 (en) 2016-11-09 2021-12-28 Novvi Llc Synthetic oligomer compositions and methods of manufacture
US11332690B2 (en) 2017-07-14 2022-05-17 Novvi Llc Base oils and methods of making the same
US11473028B2 (en) 2017-07-14 2022-10-18 Novvi Llc Base oils and methods of making the same

Families Citing this family (27)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9522854B2 (en) * 2009-07-29 2016-12-20 The United States Of America As Represented By The Secretary Of The Navy Process and apparatus for the selective dimerization of terpenes and poly-alpha-olefins with a single-stage reactor and a single-stage fractionation system
KR101984342B1 (ko) * 2011-12-30 2019-05-30 다우 글로벌 테크놀로지스 엘엘씨 파네센 기재 올리고머를 갖는 유전 유체
CN105143407B (zh) * 2013-03-15 2018-04-20 艾伯塔大学校董事会 在烯烃存在下的热解反应
CN105722960B (zh) 2013-06-28 2019-04-30 卡斯特罗尔有限公司 含有基于异戊二烯的组分的润滑组合物
MX2016000709A (es) 2013-07-17 2016-04-13 Bp Exploration Operating Metodo de recuperacion de crudo.
EP3120368A4 (fr) * 2014-03-17 2017-11-22 Novvi LLC Liquide diélectrique et liquide de refroidissement constitués d'huile de base d'origine biologique
EP3155079A4 (fr) * 2014-06-12 2017-11-22 Novvi LLC Huile de compresseur contenant une huile de base biosourcée
US20170121630A1 (en) * 2014-06-12 2017-05-04 Novvi Llc Hydraulic fluids from renewable isoparaffins
EP3278038A1 (fr) * 2015-03-30 2018-02-07 Carrier Corporation Réfrigérants à faible teneur en huile et systèmes de compression de vapeur
US20180119033A1 (en) * 2015-05-08 2018-05-03 Novvi Llc Process for the manufacture of base oil
EP3095839A1 (fr) 2015-05-20 2016-11-23 Total Marketing Services Procédé pour la production de fluides hydrocarbonés biodégradables par hydrogénation
WO2017053569A1 (fr) * 2015-09-23 2017-03-30 Amyris, Inc. Compositions et procédés pour l'extraction de composés botaniques à partir de plantes
US10093594B2 (en) 2016-05-19 2018-10-09 Chevron U.S.A. Inc. High viscosity index lubricants by isoalkane alkylation
US9822046B1 (en) * 2016-05-19 2017-11-21 Chevron U.S.A. Inc. Farnesane alkylation
EP3487959A4 (fr) 2016-07-25 2020-02-19 The Governors of the University of Alberta Procédés de production de compositions d'hydrocarbures à indice d'acidité réduit et d'isolement d'acides gras à chaîne courte
GB2567198B (en) * 2017-10-05 2022-01-12 Scott Bader Co Inverse emulsion thickeners
ES2967511T3 (es) 2018-05-01 2024-04-30 Novvi Llc Mezcla de hidrocarburos que muestra una estructura de ramificación única
US10961167B2 (en) 2018-09-20 2021-03-30 Novvi Llc Process for preparing hydrocarbon mixture exhibiting unique branching structure
KR20220047299A (ko) 2019-08-14 2022-04-15 셰브런 유.에스.에이.인크. 재생가능 윤활유 조성물을 이용한 엔진 성능 개선 방법
CN110804476B (zh) * 2019-11-02 2022-02-11 华东师范大学 一种生物质基低粘度全合成润滑油的制备方法
BR112022011826A2 (pt) 2019-12-18 2022-08-30 Lubrizol Corp Composto de tensoativo polimérico
US20230167378A1 (en) 2020-04-10 2023-06-01 Chevron Oronite Company Llc Lubricating oil compositions comprising biobased base oils
US20220127545A1 (en) 2020-10-28 2022-04-28 Chevron U.S.A. Inc. Lubricating oil composition with renewable base oil
US11906505B2 (en) * 2021-02-12 2024-02-20 Chevron U.S.A. Inc. Method of determining renewable carbon content while producing and blending biogenic-based fuels or blendstocks with fossil fuel in a refining or blending facility
KR20240053581A (ko) 2021-07-21 2024-04-24 이볼브 루브리컨츠, 인크. 재생가능한 오일로부터 석유 대체물 및 그를 포함하는 윤활제로의 다수의 생성물 경로
US20230092322A1 (en) 2021-09-09 2023-03-23 Chevron U.S.A. Inc. Renewable Based E-Drive Fluids
WO2023059603A2 (fr) * 2021-10-05 2023-04-13 Celanese International Corporation Procédé de fabrication d'acide sorbique à partir de matériaux renouvelables

Citations (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2417220A (en) * 1944-03-11 1947-03-11 Univ Manufacture of 2,6-dimethylheptanoic acid
US2674634A (en) 1950-08-05 1954-04-06 Shell Dev Hydrogenation of polyunsaturated compounds
US3702348A (en) 1969-10-20 1972-11-07 Huels Chemische Werke Ag Process for the preparation of saturated monocyclic monoterpenes
US4546110A (en) 1981-05-28 1985-10-08 National Research Development Corporation Pheromones
US4590319A (en) 1984-03-06 1986-05-20 Mitsubishi Chemical Industries, Ltd. Method for the partial hydrogenation of conjugated dienes
US5151172A (en) 1991-05-03 1992-09-29 Amoco Corporation Distillate hydrogenation
US5378767A (en) 1993-06-18 1995-01-03 Shell Oil Company Fixed bed hydrogenation of low molecular weight polydiene polymers
US6403844B1 (en) 1998-11-24 2002-06-11 Board Of Trustees Of Michigan State University Condensed phase catalytic hydrogenation of lactic acid to propylene glycol
WO2007139924A2 (fr) 2006-05-26 2007-12-06 Amyris Biotechnologies, Inc. Dispositif de fabrication de composés bio-organiques
WO2007140339A2 (fr) 2006-05-26 2007-12-06 Amyris Biotechnologies, Inc. Production d'isoprénoïdes
US7399323B2 (en) 2006-10-10 2008-07-15 Amyris Biotechnologies, Inc. Fuel compositions comprising farnesane and farnesane derivatives and method of making and using same
US20090137014A1 (en) 2007-09-20 2009-05-28 Hiroko Tsuruta Production of isoprenoids
WO2010042208A2 (fr) 2008-10-10 2010-04-15 Amyris Biotechnologies, Inc. Dimères de farnésène et/ou de farnésane et leurs compositions
WO2010115097A2 (fr) * 2009-04-02 2010-10-07 Amyris Biotechnologies, Inc Procédés de stabilisation et d'hydrogénation pour oléfines de dérivés microbiens
US20110287988A1 (en) 2010-05-21 2011-11-24 Karl Fisher Squalane and isosqualane compositions and methods for preparing the same

Family Cites Families (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB693407A (en) * 1950-08-05 1953-07-01 Bataafsche Petroleum Improvements in and relating to the partial hydrogenation of polyunsaturated organiccompounds
NL6503362A (fr) 1965-03-17 1966-09-19
US3475509A (en) 1966-09-19 1969-10-28 Toray Industries Process for producing non-conjugated dienes
US3987121A (en) * 1975-08-26 1976-10-19 International Flavors & Fragrances Inc. Process for separating alpha-pinene from beta-pinene
US4310714A (en) * 1980-12-10 1982-01-12 Union Camp Corporation Hydrogenation of α-pinene to cis-pinane
US5153157A (en) 1987-01-30 1992-10-06 Exxon Chemical Patents Inc. Catalyst system of enhanced productivity
US5198401A (en) 1987-01-30 1993-03-30 Exxon Chemical Patents Inc. Ionic metallocene catalyst compositions
US5241025A (en) 1987-01-30 1993-08-31 Exxon Chemical Patents Inc. Catalyst system of enhanced productivity
US5118837A (en) * 1987-02-12 1992-06-02 Givaudan Corporation Selective hydrogenation of olefins
US5208405A (en) * 1992-03-03 1993-05-04 Phillips Petroleum Company Selective hydrogenation of diolefins
US5723709A (en) * 1994-04-14 1998-03-03 Arizona Chemical Company Terpene dimer compositions and related methods of manufacture
US5475173A (en) * 1994-07-19 1995-12-12 Phillips Petroleum Company Hydrogenation process and catalyst therefor
DE69923816T2 (de) 1998-08-26 2006-02-09 Takasago International Corp. Dienverbindungen sowie Verfahren zu deren Herstellung
EP1216991A1 (fr) * 2000-12-22 2002-06-26 Akzo Nobel N.V. Compositions de péroxides organiques transportables contenant des flegmatisants réactifs et leur emballage de sécurité
JP4933089B2 (ja) * 2005-05-12 2012-05-16 出光興産株式会社 潤滑油組成物の製造方法
BRPI0716954B1 (pt) 2006-09-26 2024-04-30 The Regents Of The University Of California Microrganismos geneticamente modificados capazes de produzir um isoprenóide
US8217128B2 (en) 2008-09-04 2012-07-10 Amyris, Inc. Farnesene interpolymers
US9040630B2 (en) 2010-08-02 2015-05-26 Amyris, Inc. Graft copolymers of polyfarnesenes with condensation polymers
WO2012141783A1 (fr) 2011-04-13 2012-10-18 Amyris, Inc. Oléfines et procédés de fabrication desdites oléfines
WO2013028307A1 (fr) 2011-08-24 2013-02-28 Amyris, Inc. Dérivés de terpènes hydrocarbonés

Patent Citations (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2417220A (en) * 1944-03-11 1947-03-11 Univ Manufacture of 2,6-dimethylheptanoic acid
US2674634A (en) 1950-08-05 1954-04-06 Shell Dev Hydrogenation of polyunsaturated compounds
US3702348A (en) 1969-10-20 1972-11-07 Huels Chemische Werke Ag Process for the preparation of saturated monocyclic monoterpenes
US4546110A (en) 1981-05-28 1985-10-08 National Research Development Corporation Pheromones
US4590319A (en) 1984-03-06 1986-05-20 Mitsubishi Chemical Industries, Ltd. Method for the partial hydrogenation of conjugated dienes
US5151172A (en) 1991-05-03 1992-09-29 Amoco Corporation Distillate hydrogenation
US5378767A (en) 1993-06-18 1995-01-03 Shell Oil Company Fixed bed hydrogenation of low molecular weight polydiene polymers
US6403844B1 (en) 1998-11-24 2002-06-11 Board Of Trustees Of Michigan State University Condensed phase catalytic hydrogenation of lactic acid to propylene glycol
WO2007139924A2 (fr) 2006-05-26 2007-12-06 Amyris Biotechnologies, Inc. Dispositif de fabrication de composés bio-organiques
WO2007140339A2 (fr) 2006-05-26 2007-12-06 Amyris Biotechnologies, Inc. Production d'isoprénoïdes
US20080274523A1 (en) 2006-05-26 2008-11-06 Neil Stephen Renninger Production of isoprenoids
US7659097B2 (en) 2006-05-26 2010-02-09 Amyris Biotechnologies, Inc. Production of isoprenoids
US7399323B2 (en) 2006-10-10 2008-07-15 Amyris Biotechnologies, Inc. Fuel compositions comprising farnesane and farnesane derivatives and method of making and using same
US20090137014A1 (en) 2007-09-20 2009-05-28 Hiroko Tsuruta Production of isoprenoids
WO2010042208A2 (fr) 2008-10-10 2010-04-15 Amyris Biotechnologies, Inc. Dimères de farnésène et/ou de farnésane et leurs compositions
WO2010115097A2 (fr) * 2009-04-02 2010-10-07 Amyris Biotechnologies, Inc Procédés de stabilisation et d'hydrogénation pour oléfines de dérivés microbiens
US20110287988A1 (en) 2010-05-21 2011-11-24 Karl Fisher Squalane and isosqualane compositions and methods for preparing the same

Non-Patent Citations (13)

* Cited by examiner, † Cited by third party
Title
"J. Res. Natl. Stand. Technol.", vol. 100, 1995, article "New IUPAC guidelines for the reporting of stable hydrogen, carbon, and oxygen isotope-ratio data", pages: 285
ANET E.F.L.J.: "Synthesis of (E,Z)-a-, and (Z)-(3-farnesene", AUST. J. CHEM., vol. 23, no. 10
DIEGUEZ ET AL.: "Weakening C-O Bonds: Ti(III), a New Regaent for Alcohol Deoxygenation and Carbonyl Coupling Olefination", J. AM. CHEM. SOC., vol. 132, 2010, pages 254 - 259, XP055301686, DOI: doi:10.1021/ja906083c
HERNANDEZ-TORRES ET AL: "Stereocontrolled generation of the (2R) chroman core of vitamin E: total synthesis of (2R,4'RS,8'RS)-alpha-tocopherol", ORGANIC LETTERS., vol. 11, no. 21, 1 January 2009 (2009-01-01), USACS, WASHINGTON, DC., pages 4930 - 4933, XP002682061, ISSN: 1523-7060 *
JONG TAE LEE ET AL.: "Regioselective hydrogenation of conjugated dienes catalyzed by hydridopentacyanocobaltate anion using f3-cyclodextrin as the phase transfer agent and lanthanide halides as promoters", J. ORG. CHEM., vol. 55, no. 6, 1990, pages 1854 - 1856, XP002628319, DOI: doi:10.1021/jo00293a034
JONG TAE LEE ET AL.: "Regioselective hydrogenation of conjugated dienes catalyzed by hydridopentacyanocobaltate anion using l3-cyclodextrin as the phase transfer agent and lanthanide halides as promoters", J. ORG. CHEM., vol. 55, no. 6, 1990, pages 1854 - 1856, XP002628319, DOI: doi:10.1021/jo00293a034
M. STUIVER; S.W. ROBINSON, EARTH AND PLANETARY SCIENCE LETTERS, vol. 23, pages 87 - 90
SMITH, L. E. AND ROUAULT, G. F., J. AM. CHEM. SOC., vol. 65, 1943, pages 745 - 750
TUNGLER ET AL.: "Patai's Chemistry of Functional Groups", 15 December 2009, JOHN WILEY AND SONS, LTD, article "Reduction of Dienes and Polyenes"
TUNGLER ET AL.: "The Chemistry of Dienes and Polyenes", vol. 2, 2003, JOHN WILEY & SONS, LTD, article "Reduction of Dienes and Polyenes"
TUNGLER, A.; HEGEDIIS, L.; FODOR, K.; FARKAS, G.; FIIRCHT, A.; KARANCSI, Z. P.: "Patai's Chemistry of Functional Groups", 15 December 2009, JOHN WILEY AND SONS, LTD, article "Reduction of Dienes and Polyenes"
TUNGLER, A.; HEGEDIIS, L.; FODOR, K.; FARKAS, G.; FIIRCHT, A.; KARANCSI, Z. P.: "The Chemistry of Dienes and Polyenes", vol. 2, 2003, JOHN WILEY & SONS, LTD, article "Reduction of Dienes and Polyenes"
V. M. FROLOV ET AL.: "Highly active supported palladium catalysts for selective hydrogenation of conjugated dienes into olefins", REACTION KINETICS AND CATALYSIS LETTERS, vol. 25, no. 3-4, 1984, pages 319 - 322

Cited By (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9862906B2 (en) 2011-04-13 2018-01-09 Amyris, Inc. Base oils and methods for making the same
CN105122380A (zh) * 2013-02-21 2015-12-02 Abb技术有限公司 可再生烃基绝缘流体
US10071034B2 (en) 2014-05-02 2018-09-11 Amyris, Inc. Solvent compositions
WO2015168658A1 (fr) * 2014-05-02 2015-11-05 Amyris, Inc. Compositions de solvant à base de dihydrofarnésène
US20170305819A1 (en) * 2014-10-20 2017-10-26 Novvi Llc Selective partial hydrogenation of beta-farnesene
WO2016064853A1 (fr) * 2014-10-20 2016-04-28 Novvi Llc Hydrogénation partielle sélective de bêta-farnesène
EP3209630A4 (fr) * 2014-10-20 2018-05-30 Novvi LLC Hydrogénation partielle sélective de bêta-farnesène
WO2016177866A1 (fr) * 2015-05-07 2016-11-10 Total Marketing Services Hydrogénation sélective de terpènes à l'aide d'un catalyseur à base d'iridium
WO2016177868A1 (fr) 2015-05-07 2016-11-10 Total Marketing Services Hydrogénation partielle sélective de terpènes à l'aide d'un catalyseur à base de nickel
WO2017059136A1 (fr) * 2015-10-02 2017-04-06 Amyris, Inc. Compositions contenant du farnesène à base de biomatériau ou composés dérivés de celui-ci et leur utilisation dans des produits de consommation et industriels
US10695273B2 (en) 2015-10-02 2020-06-30 Amyris, Inc. Compositions containing bio-based farnesene or compounds derived therefrom and their use in consumer and industrial products
US11208607B2 (en) 2016-11-09 2021-12-28 Novvi Llc Synthetic oligomer compositions and methods of manufacture
CN107153091A (zh) * 2017-05-31 2017-09-12 中国科学院地球化学研究所 植物同化铵盐的无机氮同位素分馏值的测定方法
CN107153091B (zh) * 2017-05-31 2019-09-27 中国科学院地球化学研究所 植物同化铵盐的无机氮同位素分馏值的测定方法
US11332690B2 (en) 2017-07-14 2022-05-17 Novvi Llc Base oils and methods of making the same
US11473028B2 (en) 2017-07-14 2022-10-18 Novvi Llc Base oils and methods of making the same

Also Published As

Publication number Publication date
EP2697186A1 (fr) 2014-02-19
US9862906B2 (en) 2018-01-09
US20240043356A1 (en) 2024-02-08
BR112013026417B1 (pt) 2021-11-09
US20140148624A1 (en) 2014-05-29
US11193078B2 (en) 2021-12-07
WO2012141783A4 (fr) 2012-12-20
BR112013026416A2 (pt) 2020-11-10
US11802100B2 (en) 2023-10-31
BR112013026416B1 (pt) 2021-11-09
US20220154092A1 (en) 2022-05-19
EP2697187B1 (fr) 2020-04-22
US10294439B2 (en) 2019-05-21
US20190249101A1 (en) 2019-08-15
BR112013026417A2 (pt) 2020-11-03
US20140221258A1 (en) 2014-08-07
WO2012141784A1 (fr) 2012-10-18
PT2697187T (pt) 2020-06-16
EP2697187A1 (fr) 2014-02-19
EP2697186B1 (fr) 2018-05-23

Similar Documents

Publication Publication Date Title
US11802100B2 (en) Olefins and methods for making the same
US10183901B2 (en) Stabilization and hydrogenation methods for microbial-derived olefins
Molnár et al. Hydrogenation of carbon–carbon multiple bonds: chemo-, regio-and stereo-selectivity
US8933282B2 (en) Fuel compositions comprising isoprene derivatives
Biermann et al. Synthesis of alkyl‐branched fatty acids
JP2021517147A (ja) アルコール脱水によるオレフィンの調製、およびポリマー、燃料または燃料添加剤を製造するためのその使用
Liu et al. Alkylation of lignin-derived aromatic oxygenates with cyclic alcohols on acidic zeolites
US20170305819A1 (en) Selective partial hydrogenation of beta-farnesene
US9682897B1 (en) High density fuels from oxygenated terpenoids
EP2766327B1 (fr) Procédé de préparation d'un carburant aviation à partir de molécules dérivées d'une biomasse

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 12708189

Country of ref document: EP

Kind code of ref document: A1

DPE1 Request for preliminary examination filed after expiration of 19th month from priority date (pct application filed from 20040101)
NENP Non-entry into the national phase

Ref country code: DE

WWE Wipo information: entry into national phase

Ref document number: 2012708189

Country of ref document: EP

REG Reference to national code

Ref country code: BR

Ref legal event code: B01A

Ref document number: 112013026417

Country of ref document: BR

WWE Wipo information: entry into national phase

Ref document number: 14112235

Country of ref document: US

ENP Entry into the national phase

Ref document number: 112013026417

Country of ref document: BR

Kind code of ref document: A2

Effective date: 20131014